WO2003085680A1 - Electrolyte solide, convertisseur photoelectrique et procede pour produire celui-ci - Google Patents

Electrolyte solide, convertisseur photoelectrique et procede pour produire celui-ci Download PDF

Info

Publication number
WO2003085680A1
WO2003085680A1 PCT/JP2003/004562 JP0304562W WO03085680A1 WO 2003085680 A1 WO2003085680 A1 WO 2003085680A1 JP 0304562 W JP0304562 W JP 0304562W WO 03085680 A1 WO03085680 A1 WO 03085680A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
electrolyte
dye
solar cell
sensitized solar
Prior art date
Application number
PCT/JP2003/004562
Other languages
English (en)
Japanese (ja)
Inventor
Masahiro Morooka
Yusuke Suzuki
Kazuhiro Noda
Original Assignee
Sony Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sony Corporation filed Critical Sony Corporation
Priority to EP03717557A priority Critical patent/EP1494246B1/fr
Priority to AU2003227481A priority patent/AU2003227481A1/en
Priority to US10/511,012 priority patent/US7880082B2/en
Priority to KR1020047016187A priority patent/KR101005570B1/ko
Publication of WO2003085680A1 publication Critical patent/WO2003085680A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2009—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005—Photoelectrochemical storage cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/902—Particulate material prepared from an isocyanate

Definitions

  • the present invention relates to a solid electrolyte, and particularly to a solid electrolyte having excellent conductive properties and excellent reliability, a photoelectric conversion element using the same, and a manufacturing document thereof.
  • solar cells which are photoelectric conversion elements that convert sunlight into electric energy, use sunlight as an energy source, and therefore have very little impact on the global environment, and are expected to become more widely used.
  • amorphous silicon-based solar cells have lower conversion efficiency than crystalline silicon-based solar cells, higher light absorption compared to crystalline silicon-based solar cells, a wider selection range of substrates, and easier area enlargement.
  • Amorphous silicon solar cells are higher in productivity than crystalline silicon solar cells, but require a vacuum process, and the burden on facilities is still large.
  • this solar cell provides an inexpensive oxide semiconductor such as titanium oxide, the light absorption of the sensitizing dye extends over a wide visible light wavelength range up to 800 nm, and the quantum efficiency of photoelectric conversion increases. High energy conversion efficiency. Also, since there is no vacuum process, no large-scale equipment is required for production.
  • an electrochemical photovoltaic cell is of a wet type, and thus lacks reliability, for example, due to leakage of the electrolyte and deterioration of characteristics due to volatilization of the electrolyte.
  • a gel electrolyte in which an electrolyte is impregnated into a polymer such as polyethylene oxide (PEO) has been proposed, but the viscosity of the electrolyte is high and nano-sized oxide semiconductor particles are used for the electrode. Because It is difficult to impregnate the inside of the electrode pores with the electrolyte, and the problem is that the photovoltaic conversion efficiency is reduced due to low conductive properties.
  • the cross-linking points of the gel electrolyte form a gel by secondary weak interaction such as intermolecular force between the polymers, there is a problem that the gel electrolyte is easily liquefied by heating.
  • a coating step and a step of removing a low-boiling point and low-viscosity solvent are required during film formation, there is a problem that productivity is poor.
  • the gel electrolyte is characterized in that the viscosity of the monomer and the plasticizer solution before polymerization is low, and the electrolyte easily penetrates into the electrode pores.
  • a monomer solution obtained by dissolving a polyfunctional monomer in an electrolyte solution is injected into a previously prepared device, and gelled in situ, so that the chemical bonding at the electrode interface is good and the photoelectric conductivity is good.
  • a conversion element can be obtained.
  • an ionic liquid, ie, a molten salt instead of the electrolytic solution using a solvent, it is possible to realize a gel electrolyte having no vapor pressure.
  • iodine acts as a polymerization inhibitor. Therefore, in the case of an electrolytic solution containing iodine redox as a carrier for charge transfer, there is a problem that gelation cannot be performed with in situ.
  • the present invention has been made in view of the above-mentioned conventional circumstances, and has a solid electrolyte having good conductivity and excellent reliability, a photoelectric conversion element using the same, and a method for producing the same.
  • the purpose is to provide. Disclosure of the invention
  • the present invention solves the above-mentioned problem by a new polymerization method that does not use a radical polymerization method.
  • the solid electrolyte according to the present invention that achieves the above object is a solid electrolyte having an electrolyte composition and a matrix polymer, wherein the matrix polymer has a first compound having two or more isocyanate groups, It is assumed that the second compound having two or more nucleophilic groups having hydrogen is polymerized by a polyaddition reaction, and that the solid electrolyte is brought into contact with the surface prior to polymerization and then polymerized. It is a feature.
  • Another solid electrolyte according to the present invention that achieves the above object is a solid electrolyte having an electrolyte composition and a matrix polymer, wherein the matrix polymer has a first polymer having two or more unsaturated double bonds.
  • the compound and a second compound having two or more nucleophilic groups having active hydrogen are polymerized by a Michael addition reaction, and are brought into contact with a surface forming a solid electrolyte in a state before polymerization, and then polymerized. It is characterized by becoming.
  • the redox pair is preferably used for a photoelectric conversion element in which a combination of a halogen ion and a halide ion is used.
  • a photoelectric conversion element according to the present invention that achieves the above object includes a semiconductor layer made of semiconductor particles carrying a dye and an electrolyte layer between an electrode formed on the surface of a transparent substrate and a counter electrode.
  • a photoelectric conversion element wherein the electrolyte layer has a redox couple, an electrolyte composition, and a matrix polymer, and the matrix polymer has a first compound having two or more isocyanate groups and a nucleophilic group having active hydrogen. Is formed by a polyaddition reaction with a second compound having two or more of T JP03 / 04562
  • another photoelectric conversion element that achieves the above object includes a semiconductor layer made of semiconductor particles carrying a dye between an electrode formed on the surface of a transparent substrate and a counter electrode, and an electrolyte.
  • a photoelectric conversion device comprising: a first compound having a redox couple, an electrolyte composition, and a matrix polymer, wherein the matrix polymer has two or more unsaturated double bonds.
  • a second compound having two or more nucleophilic groups having active hydrogen are polymerized by a Michael addition reaction, and are brought into contact with a surface on which a solid electrolyte is formed in a state before polymerization, and then polymerized. It is characterized by the following.
  • the above-described photoelectric conversion element according to the present invention is suitable when the above-mentioned redox pair is a combination of a halide ion and a halide ion, and even in that case, it is particularly suitable when the halogen element is iodine. It is.
  • a method for manufacturing a photoelectric conversion element according to the present invention includes a semiconductor layer made of semiconductor particles carrying a dye and an electrolyte layer between an electrode formed on the surface of a transparent substrate and a counter electrode.
  • a method for producing a photoelectric conversion element comprising: a first compound having two or more isocyanate groups and two or more nucleophilic groups having active hydrogen after assembling the photoelectric conversion element.
  • a mixed solution containing a second compound and an electrolyte composition containing a redox pair is introduced into the photoelectric conversion element, and the first compound and the second compound are subjected to a polyaddition reaction in the photoelectric conversion element. It is characterized by being polymerized and solidified to form the above-mentioned electrolyte layer.
  • another method for manufacturing a photoelectric conversion element according to the present invention includes a method of forming a semiconductor layer made of semiconductor particles carrying a dye between an electrode formed on a surface of a transparent substrate and a counter electrode.
  • Photoelectric conversion comprising an electrolyte layer
  • a method for producing a conversion element comprising: after assembling a photoelectric conversion element, a first compound having two or more unsaturated double bonds, and a second compound having two or more nucleophilic groups having active hydrogen.
  • a mixed solution containing an electrolyte composition containing a redox couple is introduced into the photoelectric conversion element, and the first compound and the second compound are polymerized by a Michael addition reaction in the photoelectric conversion element to be solidified;
  • the method is characterized in that the electrolyte layer is formed.
  • FIG. 1 is a cross-sectional view showing one structural example of a dye-sensitized solar cell constituted by applying the present invention.
  • FIG. 2 is a cross-sectional view showing another configuration example of the dye-sensitized solar cell configured by applying the present invention.
  • FIG. 3 is a cross-sectional view showing another configuration example of the dye-sensitized solar cell configured by applying the present invention.
  • FIG. 4 is a cross-sectional view showing another configuration example of the dye-sensitized solar cell configured by applying the present invention.
  • the solid electrolyte according to the present invention a photoelectric conversion element using the same, and a method for producing the same will be described in detail.
  • the present invention is not limited to the following description, and can be appropriately modified without departing from the gist of the present invention.
  • the solid electrolyte according to the present invention is a solid electrolyte having an electrolyte composition and a matrix polymer, wherein the matrix polymer is an isocyanate group. And a second compound having two or more nucleophilic groups having active hydrogen are polymerized by a polyaddition reaction, and the surface on which a solid electrolyte is formed is not polymerized. It is characterized in that it contacts in a state and then polymerizes.
  • FIG. 1 is a cross-sectional view illustrating a configuration of a dye-sensitized solar cell which is a photoelectric conversion element configured by applying the above-described present invention.
  • a dye-sensitized solar cell 1 includes a transparent substrate 2, a transparent electrode 3, a semiconductor layer 4, a solid electrolyte 5, a platinum chloride-treated platinum layer 6, a transparent electrode 7, and a transparent substrate 8. It is configured with.
  • the transparent substrate 2 and the transparent substrate 8 are not particularly limited as long as they have transparency, and for example, a glass substrate can be used.
  • the transparent electrode 3 and the transparent electrode 7 are electrodes formed on the lower surface of the transparent substrate 2 with a transparent material.
  • a transparent material any material having conductivity and transparency can be used, but tin is preferred because of its high level of conductivity, transparency and heat resistance.
  • a system oxide is preferable, and IT0 is preferable in terms of cost.
  • the transparent electrode 7 is not necessarily provided, and may be formed as needed.
  • the semiconductor layer 4 is obtained by sintering semiconductor particles carrying a dye on the transparent electrode 3, and the dye absorbs light that has passed through the transparent substrate 2 and the transparent electrode 3 and entered the semiconductor layer 4.
  • the semiconductor particles are semiconductor fine particles to which a dye is adsorbed.
  • a compound semiconductor or a compound having a perovskite structure can be used.
  • These semiconductors are preferably n-type semiconductors in which conduction band electrons serve as carriers under photoexcitation to give an anode current.
  • T i S R_ ⁇ 3 is like, particularly preferably a T i ⁇ 2 ANATA one peptidase type.
  • the types of semiconductors are not limited to these, and they may be used alone or in combination of two or more.
  • the method for forming the semiconductor layer 4 is not particularly limited.However, in consideration of physical properties, convenience, manufacturing costs, and the like, a wet film forming method for semiconductor fine particles is preferable. It is preferable to prepare a paste uniformly dispersed in a solvent and apply the paste on a substrate on which a transparent conductive film is formed.
  • the coating method is not particularly limited and can be performed according to a known method.Examples include a dip method, a spray method, a wire bar method, a spin coating method, a mouth coating method, a blade coating method, a gravure coating method, and the like.
  • As the wet printing method various methods such as letterpress, offset, gravure, intaglio, rubber plate, screen printing, etc. can be used.
  • the crystalline form of titanium oxide is preferably anatase type from the viewpoint of photocatalytic activity.
  • the anatase type titanium oxide may be a commercially available powder, sol, or slurry, or may have a predetermined particle size by a known method such as hydrolysis of titanium oxide alkoxide.
  • a commercially available powder it is preferable to eliminate the secondary aggregation of the particles, and it is preferable to grind the particles using a mortar, a pole mill, or the like when preparing the coating solution.
  • acetylacetone, hydrochloric acid, nitric acid, a surfactant, a chelating agent, and the like can be added to prevent the particles having been subjected to secondary aggregation from reaggregating.
  • various thickeners such as polymers such as polyethylene oxide and polyvinyl alcohol, and cellulose-based thickeners can also be added.
  • the average particle size of the primary particles is preferably from 1 to 200 nm, particularly preferably from 5 to 100 nm.
  • two or more kinds of particles having a size larger than the above semiconductor fine particles are mixed.
  • the average size of the particles to be separately mixed is preferably from 20 to 500 nm.
  • the semiconductor layer preferably has a large surface area so that many dyes can be adsorbed.
  • the surface area in a state where the semiconductor fine particles are coated on the support is preferably at least 10 times, more preferably at least 100 times the projected area. There is no particular upper limit, but it is usually about 1000 times.
  • the semiconductor layer has a preferable thickness, it is generally 0.1 / 2 m to 100 m, more preferably 1 m to 50 m, and 3! It is particularly preferred that the distance is 30 m.
  • the semiconductor fine particles be applied to a support, then electronically contact the particles, and fired to improve the film strength and the adhesion to the substrate.
  • the range of the firing temperature There is no particular limitation on the range of the firing temperature.However, if the temperature is too high, the resistance of the substrate increases, and the substrate may be melted. It is 40 ° C to 65 ° C.
  • the firing time is not particularly limited, but is usually about 10 minutes to 10 hours.
  • the dye adsorbed on the semiconductor fine particles for example, a ruthenium dye is preferable.
  • the dye adsorbed on the semiconductor fine particles is not particularly limited as long as it has a charge separation function and exhibits a sensitizing effect.
  • ruthenium dyes for example, xanthene dyes such as rhodamine B, rose bengal, eosin, and erythrin, cyanine dyes such as quinosine and cryptosyanine, phenosafranine, cabrio blue, thiocyanine, and methylene blue First-class basic dyes, porphyrin compounds such as chlorophyll, zinc porphyrin, magnesium porphyrin, other azo dyes, phthalocyanine compounds, complex compounds such as Ru trisbipyridyl, anthraquinone dyes, Examples thereof include polycyclic quinone dyes, and these can be used alone or in combination of two or more.
  • the above dye includes alcohols, nitriles, nitromethane, halogenated hydrocarbons, ethers, dimethyl sulfoxide, amides, N-methylpyrrolidone, Dissolve in a solvent such as 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, esters, carbonates, ketones, hydrocarbons, and water, and immerse the electrode with the semiconductor layer, or dye A solution can be applied to the semiconductor layer.
  • Deoxycholic acid, chenodeoxycholic acid, etc. may be added for the purpose of reducing the association between dyes.
  • an ultraviolet absorber can be used in combination.
  • the surface of the semiconductor fine particles may be treated with an amine after adsorbing the dye.
  • amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine and the like. When these are liquid, they may be used as they are, or may be used by dissolving them in an organic solvent.
  • the solid electrolyte 5 is composed of a gel electrolyte or a complete solid electrolyte to be a carrier transfer layer, and a first compound having two or more isocyanate groups and a second compound having two or more nucleophilic groups having active hydrogen. To polymerize by a polyaddition reaction with the compound of Features. Therefore, in this dye-sensitized solar cell, by using a solid electrolyte 5 consisting of a gel electrolyte or a completely solid electrolyte for such an electrolyte layer, the electrolyte due to liquid leakage or volatilization caused when the electrolyte is used is used. Layer reduction is prevented, and a dye-sensitized solar cell with excellent battery characteristics and reliability has been realized.
  • One of the first compound and the second compound preferably has ether, ester, carbonate, alkyl, perfluorocarbon, nitrile, tertiary amine, or the like in the main chain and side chain.
  • the number of isocyanate groups in the first compound is preferably two or more, but when the number of nucleophilic groups having active hydrogen in the second compound is two, the number of isocyanate groups in the first compound is Requires 3 or more.
  • the number of nucleophilic groups having active hydrogen in the second compound is preferably two or more, but when the number of isocyanate groups in the first compound is two, the number in the second compound is At least three nucleophilic groups having active hydrogen are required.
  • compounds having different skeletons may be used alone or in combination of two or more.
  • the first compound include tolylene 2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated 4,4'-diphenyl. Trimer of methanediisocyanic acid, hexamethylene diisocyanate, polymer of isocyanateethyl methacrylate, and the like. In order to improve the light fastness, it is preferable to select an aliphatic isocyanate compound as the first compound, and these can be used alone or in combination of two or more.
  • the second compound examples include polyol compounds such as diol, triol, and tetraol; similarly, polyamine compounds such as diamine, triamine, and tetraamine; dicarboxylic acid, tricarboxylic acid, and the like.
  • Polycarboxylic acids such as tetracarboxylic acid and the like can be mentioned, and these can be used alone or in combination of two or more.
  • a catalyst may be used to efficiently promote the polyaddition reaction.
  • the catalyst include tin catalysts such as dibutyltin dilauric acid and amine catalysts, which are known for polyurethane synthesis.
  • the present invention is not limited thereto, and these can be used alone or in combination of two or more.
  • the amount of the catalyst added is 1 t% or less, preferably 0.1 wt% or less.
  • the gel electrolyte 5 is a gel electrolyte
  • the gel electrolyte is composed of an electrolyte composition containing a solvent and the crosslinked matrix, and the ratio of the crosslinked matrix to the gel electrolyte is 3 wt% to 5 wt%. 0 wt%.
  • Solvents constituting the electrolyte composition include water, alcohols, ethers, esters, carbonates, lactones, carboxylate esters, phosphate triesters, heterocyclic compounds, Nitriles, ketones, amides, nitromethane, halogenated hydrocarbons, dimethylsulfoxide, sulfolane, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, hydrocarbons, etc. Examples thereof include, but are not limited to, these, and these can be used alone or in combination of two or more. Among these, a nonprotonic nonaqueous solvent is more preferable.
  • the ratio of the electrolyte composition in the gel electrolyte increases, the force at which the ionic conductivity increases increases, and the mechanical strength decreases.
  • the ratio of the electrolyte composition in the gel electrolyte 5 decreases, the mechanical strength increases but the ionic conductivity decreases.
  • the ratio of the electrolyte composition in the gel electrolyte ranges from 50 wt% to 97 w t% is preferable, and 80 wt% to 95 wt% is more preferable.
  • the electrolyte used in the gel electrolyte other combinations of I 2 and a metal iodide or an organic ® ⁇ combination of products, B r 2 and a metal bromide or an organic bromide, Fueroshian salt Z Fuerishian salt and Hue spout / Metal complexes such as ferricinium ions, sodium polysulfide, alkyl compounds such as alkylthiol Z-alkyl disulfides, piologen dyes, hydroquinone Z quinone, and the like can be used.
  • Examples of the cation of the metal compound include Li, Na, K, Mg, Ca, and Cs.
  • Examples of the cation of the organic compound include quaternary compounds such as tetraalkylammoniums, pyridiniums, and imidazoliums.
  • Ammonium compounds are suitable, but not limited thereto, and they can be used alone or as a mixture of two or more. Among them, 1 2 and L i I or Imidazoriumuyo one die de electrolyte that combines a quaternary Anmoniumu compounds of are preferred.
  • the concentration of the electrolyte salt is preferably from 0.05 M to 5 M, more preferably from 0.2 M to 1 M, based on the solvent.
  • the concentration of 12 or Br 2 is preferably from 0.005 M to 1 M, more preferably from 0.001 M to 0.1 M.
  • Various additives such as 4-tert-butylpyridine and carboxylic acid can be added for the purpose of improving the open-circuit voltage and the short-circuit current.
  • the completely solid electrolyte is composed of, for example, the crosslinked matrix containing iodine redox.
  • Metal complexes such as thiophene, sodium polysulfide, alkyl compounds such as alkylthiol / alkyl disulfide, piologen dyes, hydroquinone / 04562
  • Examples of the cation of the metal compound include Li, Na, K, Mg, Ca, and Cs.
  • Examples of the cation of the organic compound include tetraalkylammonium, pyridinium, and imidazolyme. Preferred are, but not limited to, grade ammonium compounds, and these can be used alone or in combination of two or more. Among them, 1 2 and
  • An electrolyte combining a quaternary ammonium compound such as L i I or imidazolidide is preferred.
  • the concentration of the electrolyte salt is 0.
  • the concentration of 12 ⁇ 8 1 ′′ 2 is preferably from 0.005 M to LM, more preferably from 0.001 M to 0.1 M.
  • the solid electrolyte 5 configured as described above is made of a gel electrolyte or a completely solid electrolyte, the solid electrolyte 5 is a highly reliable electrolyte without any leakage of the electrolyte, deterioration of the characteristics due to volatilization of the electrolyte, and the like.
  • the matrix polymer of the solid electrolyte 5 is a polymer obtained by the polyaddition reaction of the first compound and the second compound described above, and is chemically crosslinked. Excellent mechanical properties and durability.
  • the solid electrolyte 5 comes into contact with the surface on which the solid electrolyte is formed, that is, the electrode surface in a state before the polymerization having fluidity, and then is polymerized, so that the electrolyte is sufficiently impregnated into the pores of the electrode surface.
  • the state of the chemical interface at the electrochemical interface between the solid electrolyte and the surface of the electrode is made favorable, it has good electrical conductivity.
  • the solid electrolyte 5 is formed by polymerizing the above-described first compound and second compound by a polyaddition reaction, it is not necessary to use a thermally active light beam during the polymerization. As a result, heat and actinic rays An electrolyte having good conductivity without degradation of the degrading composition has been realized, and the manufacturing process is simple and the productivity is excellent.
  • this solid electrolyte is formed by a polyaddition reaction and does not rely on the radical polymerization method, it can be easily prepared even in a case where iodine which acts as a polymerization inhibitor is contained in the electrolyte composition in the radical polymerization method. Since it can be formed in situ in a battery element, it is suitable for a photoelectric conversion element using an iodine redox pair.
  • the platinum layer 6 is a counter electrode, and any material can be used as long as it is a conductive material. However, even if an insulating material is provided on the side facing the semiconductor electrode, this is also used. Can be used. However, it is preferable to use a material that is electrochemically stable as the electrode, and specifically, it is preferable to use platinum, gold, carbon, and the like. In order to improve the oxidation-reduction catalytic effect, it is preferable that the side facing the semiconductor electrode has a fine structure and an increased surface area. Preferably, it is in a porous state. The platinum black state can be formed by anodic oxidation of platinum or chloroplatinic acid treatment, and the porous carbon can be formed by sintering carbon fine particles or sintering an organic polymer.
  • the dye-sensitized solar cell 1 configured as described above operates as follows. Light incident from the transparent electrode 2 on the transparent electrode 3 side excites the dye carried on the surface of the semiconductor layer 4, and the dye quickly passes electrons to the semiconductor fine particles of the semiconductor layer 4. On the other hand, the dye that has lost electrons receives electrons from the ions of the gel electrolyte 5. The molecules that have passed the electrons receive the electrons again at the platinum layer 6 that is the counter electrode.
  • the dye-sensitized solar cell 1 as described above can be manufactured as follows. In the following, the case where a gel electrolyte is used as the solid electrolyte 5 is described. The case will be described as an example.
  • a transparent electrode 3 is formed on one main surface of a transparent substrate 2, and a semiconductor layer 4 supporting a dye is formed on the transparent electrode 3 to form a semiconductor electrode. Further, a transparent electrode 7 is formed on one main surface of a transparent substrate 8, and a platinum layer 6 treated with platinum chloride is formed on the transparent electrode 7. Then, the semiconductor layer 4 supporting the dye and the platinum layer 6 face each other, and the side surfaces of the transparent substrate 2 and the transparent substrate 7 are sealed so that the semiconductor electrode and the counter electrode do not contact each other.
  • the distance between the semiconductor electrode and the counter electrode is not particularly limited, but is usually 1 m to 100 z m, and more preferably 1 m to 30 ⁇ m. If the distance between the electrodes is too long, the photocurrent will decrease due to the decrease in conductivity.
  • the sealing method a material having light resistance, insulation, and moisture resistance is preferable.
  • a material having light resistance, insulation, and moisture resistance is preferable.
  • epoxy resin, ultraviolet curable resin, acrylic adhesive, ethylene vinyl acetate (EVA), ceramic, A heat fusion film or the like can be used.
  • the photoelectric conversion element of the present invention requires an injection port for injecting the solution before gelation, but the location of the injection port is not on the semiconductor layer 4 carrying the dye and the counter electrode in a portion facing the semiconductor layer 4. Is not particularly limited and can be provided at any location.
  • a mixed solution to be a precursor of the gel electrolyte 5 is prepared.
  • a second compound having two or more nucleophilic groups having active hydrogen is dissolved in an electrolyte solution which is an electrolyte composition.
  • the first compound having two or more isocyanate groups is dissolved to prepare a mixed solution before gelation.
  • the order of dissolution is not particularly limited, but the dissolution is preferably performed in the above order because the isocyanate group causes an addition reaction with iodine in the electrolyte composition.
  • the mixed solution is injected into the dye-sensitized solar cell 1 assembled above.
  • the method of injecting the mixed solution it is preferable to inject the liquid into the dye-sensitized solar cell 1 which is sealed in advance and the inlet of the mixed solution is opened. In this case, it is simple to drop several drops of the mixed solution into the injection port and inject the solution by capillary action. Further, if necessary, the mixed solution can be injected under reduced pressure. After the mixed solution is completely injected, remove the mixed solution before gelation remaining in the inlet, and seal the inlet.
  • the sealing method and if necessary, the glass plate can be sealed with a sealing agent.
  • the first compound having two or more cisocyanate groups and the second compound having two or more nucleophilic groups having active hydrogen Is preferably left standing until the polymerization by the polyaddition reaction is completed.
  • the time of standing usually, the fluidity of the mixed solution introduced into the dye-sensitized solar cell 1 completely disappears, and the time until gelation is completed is 1 minute to 48 hours. It is about. This time may vary depending on various conditions such as selection of the first compound and the second compound, selection of the electrolyte, selection of the solvent, and the like.
  • the ambient temperature at which the sample is left standing but it is usually 0 ° C to 120 ° C, and 0 ° C to 80 ° C to suppress the influence on the dye and electrolyte. Is preferred.
  • an anti-reflection (AR) treatment may be applied to the surface of the transparent substrate 2 on the light intake side in order to increase power generation efficiency.
  • the surface of the dye-sensitized solar cell 1 may be treated by a method such as grouping, texturing, or the like to improve the efficiency of use of incident light.
  • a metal or alloy having a high reflectance such as A1 or Ag may be provided on the lowermost layer of the counter electrode by sputtering or vapor deposition. It is possible.
  • the dye-sensitized solar cell 1 can be manufactured as described above.
  • the solid electrolyte 5 Since the solid electrolyte 5 is provided, the dye-sensitized solar cell with excellent reliability is realized without the leakage of the electrolyte and the deterioration of the characteristics due to the volatilization of the electrolyte.
  • the matrix polymer of the solid electrolyte 5 is a polymer obtained by polyaddition reaction of the first compound and the second compound as described above, and is chemically crosslinked, The solid electrolyte 5 is not liquefied by heat, and a dye-sensitized solar cell excellent in mechanical properties and durability is realized.
  • a solid electrolyte When a solid electrolyte is used in a dye-sensitized solar cell, a solid electrolyte is formed in advance, and the solid electrolyte is adhered to a semiconductor layer to form a dye-sensitized solar cell. That is, since the solidified surface shapes come into contact with each other, the adhesion between the semiconductor layer and the solid electrolyte is not good, and therefore, the contact between the semiconductor layer and the solid electrolyte is insufficient, so that the photoelectric conversion efficiency is low. Is reduced.
  • the solid electrolyte 5 is introduced into the dye-sensitized solar cell in a fluid state before the polymerization, and is polymerized and formed.
  • the electrolyte is sufficiently impregnated into the inside, and the adhesion between the semiconductor fine particles of the semiconductor layer 4 and the platinum layer 6 as the counter electrode and the solid electrolyte 5 can be increased.
  • it is possible to ensure sufficient contact with the solid electrolyte 5 and the electrochemical interface between the solid electrolyte 5 and the electrode surface is good, and a dye-sensitized solar cell with good photoelectric conversion characteristics is obtained. Is achieved.
  • the solid electrolyte 5 is formed by polymerization by the polyaddition reaction as described above, it is not necessary to use heat or active light rays. Therefore, since the electrolyte composition does not deteriorate due to the use of heat or actinic rays during the formation of the solid electrolyte, a photoelectric conversion element having good photoelectric conversion characteristics has been realized, and the manufacturing process is simple and the production is simple. Excellent in nature.
  • the solid electrolyte 5 is formed by polyaddition reaction and is not based on the radical polymerization method, in the radical polymerization method, iodine which acts as a polymerization inhibitor is converted into an electrolyte composition.
  • the solid electrolyte 5 can be easily formed even in the case where the solid electrolyte 5 is included, and the solid electrolyte 5 can be formed in situ in the battery element. Therefore, according to the dye-sensitized solar cell 1, a dye-sensitized solar cell having good photoelectric conversion characteristics can be easily and reliably configured.
  • a gel electrolyte having no vapor pressure can be formed by using an ionic liquid, that is, a molten salt instead of the electrolyte composition containing a solvent.
  • FIG. 2 is a cross-sectional view showing a configuration of another dye-sensitized solar cell configured by applying the present invention.
  • the dye-sensitized solar cell 11 includes a transparent substrate 2, a transparent electrode 3, a semiconductor layer 4, a solid electrolyte 15, a platinum chloride-treated platinum layer 6, a transparent electrode 7, and a transparent substrate 8. And is provided.
  • the same members as those of the dye-sensitized solar cell 1 described above are denoted by the same reference numerals as those in FIG.
  • the solid electrolyte 15 is made of a gel electrolyte serving as a carrier transfer layer, and includes a first compound having two or more isocyanate groups and a second compound having two or more nucleophilic groups having active hydrogen. Are polymerized by a polyaddition reaction, and the polymer is used as a crosslinked matrix.
  • the solid electrolyte 15 is composed of an ionic liquid containing a redox couple and 3 to 50 wt% of the crosslinked matrix.
  • the first compound or the second compound has ether, ester, carbonate, alkyl, perfluorocarbon, nitrile, tertiary amine, or the like in the main chain and side chain.
  • the number of isocyanate groups in the first compound is preferably two or more, but when the number of nucleophilic groups having active hydrogen in the second compound is two, the number of isocyanate groups in the first compound is Requires 3 or more.
  • the number of nucleophilic groups having active hydrogen in the second compound is preferably two or more, but when the number of isocyanate groups in the first compound is two, the number of active hydrogens in the second compound is At least three nucleophilic groups are required.
  • compounds having different skeletons may be used alone or in combination of two or more.
  • the first compound include tolylene 2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated 4,4'-diphenyl.
  • an aliphatic isocyanate compound as the first compound, and these can be used alone or in combination of two or more.
  • the second compound examples include polyol compounds such as diol, triol, and tetraol; similarly, polyamine compounds such as diamine, triamine, and tetraamine; dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid. Polyboronic acid, etc .; Or a mixture of two or more types.
  • a catalyst may be used to efficiently promote the polyaddition reaction.
  • the catalyst include tin-based catalysts such as dibutyltin dilaurate, amine-based catalysts, and the like. Any known materials can be used, but the materials are not limited thereto, and they can be used alone or in combination of two or more.
  • the amount of the catalyst is 1 wt% or less, and preferably 0.1 wt% or less.
  • the ionic liquid examples include a pyridinium salt, an imidazolium salt, a triazolium salt, and the like. However, the ionic liquid is not limited thereto, and these can be used alone or in combination of two or more.
  • the melting point of the ionic liquid is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and particularly preferably 60 ° C. or lower.
  • the ratio of the ionic liquid in the gel electrolyte is preferably 50 wt% to 97 wt%, more preferably 80 wt% to 95 wt%.
  • Redox couple used in the gel electrolyte of the present invention the combination of ® ⁇ product of I 2 and the ionic liquid, B r 2 and a suitable combination of bromide such as ionic liquids, and in particular I 2 and the ionic liquid are preferred.
  • concentration of the redox species is preferably from 0.1 wt% to 20 wt%, more preferably from 0.2 wt% to 5 wt%, based on the whole electrolyte.
  • the anion of the ionic liquid may be other than the above, and in this case, halogen ions such as C 11, Br—, NSC—, —, PFC 1 ⁇ CC F 3 SO 2 ) ? N-, (CFCF, SOJ
  • the redox couple may be a combination of a metal iodide or an organic iodide, a combination of Br 2 and a metal bromide or an organic bromide, or a combination of a ferric cyanate Z phenocyanate or a fenocene erythrinidium ion.
  • Metal complexes sodium polysulfide, alkyl compounds such as alkyl thiol-alkyl disulfide, piologen dyes, hydroquinone Z quinone, and the like can be used.
  • the cation of the metal compound is preferably LiNaKMgCaCs or the like, and the cation of the organic compound is preferably a quaternary ammonium compound such as a tetraalkylammonium, a pyridinium or an imidazolium.
  • the present invention is not limited to these, and these can be used alone or in combination of two or more. Among them, 1 2 and Imidazoriumuyo electrolyte which combines quaternary Anmoniumu compounds such one die de are preferred.
  • the concentration of the electrolyte salt is preferably 0.05 M 5 M, more preferably 0.2 M 1 M, with respect to the ionic liquid.
  • the concentration of 12 or Br 2 is preferably 0, 005 M 1 M, more preferably 0.001 M 0.1 M.
  • various additives such as 4-tert-butylpyridine and carboxylic acid can be added for the purpose of improving the open-circuit voltage and the short-circuit current. Since the solid electrolyte 15 configured as described above is made of a gel electrolyte, the solid electrolyte 15 is a highly reliable electrolyte without any leakage of the electrolyte and no deterioration in characteristics due to volatilization of the electrolyte.
  • the matrix polymer of the solid electrolyte 15 is the first polymer described above. It is a polymer that has undergone a polyaddition reaction between a compound and a second compound and is chemically crosslinked, so that it does not liquefy due to heat and has excellent mechanical properties and durability.
  • the solid electrolyte 15 has a fluid solid state before polymerization, that is, a solid electrolyte forming surface. That is, the solid electrolyte 15 comes into contact with the electrode surface and then polymerizes, so that the electrolyte is injected into the pores of the electrode surface. Since it is sufficiently impregnated and has a good chemical bonding state at the electrochemical interface between the solid electrolyte and the electrode surface, it has good conductive properties.
  • the solid electrolyte 15 is formed by polymerizing the first compound and the second compound by a polyaddition reaction, it is not necessary to use heat or actinic rays during the polymerization. For this reason, an electrolyte having good conductive properties without deterioration of the electrolyte composition due to heat or actinic rays at the time of formation has been realized, and the manufacturing process is simple and the productivity is excellent.
  • the solid electrolyte 15 is formed by a polyaddition reaction and is not based on the radical polymerization method, the solid electrolyte 15 can be easily prepared even in a case where iodine acts as a polymerization inhibitor in the electrolyte composition in the radical polymerization method. Since it can be formed in a battery element in situ, it is suitable for a photoelectric conversion element using an iodine redox pair.
  • the above-described dye-sensitized solar cell 11 can be manufactured as follows.
  • a transparent electrode 3 is formed on one main surface of a transparent substrate 2, and a semiconductor layer 4 supporting a dye is formed on the transparent electrode 3 to form a semiconductor electrode. Further, a transparent electrode 7 is formed on one main surface of the transparent substrate 8, and a platinum layer 6 that has been treated with platinum chloride is formed on the transparent electrode 7. Then, the semiconductor layer 4 supporting the dye and the platinum layer 6 face each other, and the side surfaces of the transparent substrate 2 and the transparent substrate 7 are sealed so that the semiconductor electrode and the counter electrode do not contact each other. At this time, the semiconductor electrode andfig ⁇ Ra
  • the distance from the counter electrode is not particularly limited, but is usually 1 m to 100 111, more preferably 1 / m to 30 x m. If the distance between the electrodes is too long, the photocurrent will decrease due to the decrease in conductivity.
  • the sealing method a material having light resistance, insulation, and moisture resistance is preferable.
  • a material having light resistance, insulation, and moisture resistance is preferable.
  • epoxy resin, ultraviolet curing resin, acrylic adhesive, ethylene vinyl acetate (EVA), ceramic, A heat fusion film or the like can be used.
  • the photoelectric conversion element of the present invention requires an injection port for injecting the solution before gelation, but the location of the injection port is not on the semiconductor layer 4 carrying the dye and the counter electrode in a portion facing the semiconductor layer 4. Is not particularly limited and can be provided at any location.
  • a mixed solution to be a precursor of the gel electrolyte 15 is prepared.
  • a first compound having two or more isocyanate groups is dissolved in an ionic liquid containing a redox pair.
  • a second compound having two or more nucleophilic groups having active hydrogen is dissolved to prepare a mixed solution before gelation.
  • the order of dissolution is not particularly limited. However, if the first compound and the second compound are directly mixed, it is not preferable because a reaction may occur rapidly and solidify as it is.
  • the mixed solution is injected into the dye-sensitized solar cell 11 assembled above.
  • the method of injecting the mixed solution but after completely dissolving these compounds, the dye-sensitized solar cell 11 is sealed in advance and the injection port of the mixed solution is opened.
  • the preferred method is In this case, it is convenient to drop several drops of the mixed solution into the injection port and inject the solution by capillary action. Further, if necessary, the mixed solution can be injected under reduced pressure. After the mixed solution is completely injected, remove the mixed solution before gelation remaining in the inlet, and seal the inlet.
  • the sealing method and if necessary, the glass plate can be sealed with a sealing agent.
  • the first compound having two or more isocyanate groups and the second compound having two or more nucleophilic groups having active hydrogen It is preferable to dispute until the polymerization by the polyaddition reaction with the second compound is completed.
  • the time for standing There is no particular limitation on the time for standing, but usually, the time until the fluidity of the mixed solution introduced into the dye-sensitized solar cell 11 completely disappears and gelation is completed is about 1 minute to 48 hours. is there. Note that this time may vary depending on conditions such as selection of the first compound, the second compound, and selection of the ionic liquid.
  • the ambient temperature for standing it is usually 0 t: up to 100 ° C, and 0 ° C to 60 ° C in order to suppress the effect on dyes and electrolytes. Is preferred.
  • the dye-sensitized solar cell 11 can be manufactured.
  • the dye-sensitized solar cell 11 configured as described above is provided with the solid electrolyte 15 described above, so that there is no leakage of the electrolyte and no reduction in characteristics due to volatilization of the electrolyte, and the reliability is excellent.
  • Dye-sensitized solar cell is realized.
  • the matrix polymer of the solid electrolyte 15 is made of a polymer obtained by a polyaddition reaction between the first compound and the second compound as described above, and is chemically crosslinked. Therefore, the solid electrolyte 15 is not liquefied by heat, and a dye-sensitized solar cell excellent in mechanical properties and durability can be realized.
  • a solid electrolyte When a solid electrolyte is used in a dye-sensitized solar cell, a solid electrolyte is formed in advance, and the solid electrolyte is adhered to a semiconductor layer to form a dye-sensitized solar cell. That is, since the solidified surface shapes come into contact with each other, the adhesion between the semiconductor layer and the solid electrolyte is not good, and therefore, the contact between the semiconductor layer and the solid electrolyte is insufficient, so that the photoelectric conversion efficiency is low. Is reduced.
  • the solid electrolyte 15 is Since the dye is introduced into the dye-sensitized solar cell in a state before polymerization having fluidity and then formed by polymerization, the inside of the pores on the electrode surface is sufficiently impregnated with the electrolyte, and the semiconductor layer It is possible to increase the adhesiveness between the solid electrolyte 15 and the platinum layer 6 which is the semiconductor fine particle and the counter electrode of 4, and to ensure sufficient contact between the semiconductor layer 4 and the solid electrolyte 15. As a result, the state of chemical bonding at the electrochemical interface between the solid electrolyte 1 and the electrode surface is improved, and a dye-sensitized solar cell having good photoelectric conversion characteristics is realized.
  • the solid electrolyte 15 is formed by polymerization by the polyaddition reaction as described above, it is not necessary to use a heat-activated ray. Therefore, since there is no deterioration of the electrolyte composition due to the use of heat or actinic rays during the formation of the solid electrolyte, a photoelectric conversion element having good photoelectric conversion characteristics has been realized, and the manufacturing process is simple and the productivity is low. Excellent.
  • the solid electrolyte 15 is formed by the addition reaction and is not based on the radical polymerization method, in the radical polymerization method, iodine acts as a polymerization inhibitor. Even when the solid electrolyte is contained in the electrolyte composition, the solid electrolyte 15 can be easily formed, and the solid electrolyte 15 can be formed in situ in the battery element. Therefore, according to the dye-sensitized solar cell 11, a dye-sensitized solar cell having good photoelectric conversion characteristics can be simply and reliably configured. Next, another solid electrolyte and a photoelectric conversion element according to the present invention and a method for producing the same will be described in detail. FIG.
  • the dye-sensitized solar cell 21 includes a transparent substrate 2, a transparent electrode 3, a semiconductor layer 4, a solid electrolyte 25, a platinum layer 6 treated with platinum chloride, a transparent electrode 7, and a transparent substrate 8. And is provided. Note that the dye-sensitized solar cell 21 described above The same members as those of the dye-sensitized solar cell 1 are denoted by the same reference numerals as those in FIG. 1, and detailed description thereof will be omitted. In the following, only the solid electrolyte 25 will be described.
  • the solid electrolyte 25 is composed of a gel electrolyte or a completely solid electrolyte that forms a carrier transfer layer.
  • the first compound having two or more unsaturated double bonds and the nucleophilic group having active hydrogen It is characterized in that a second compound having two or more is polymerized by a Michael addition reaction, and the polymer is used as a bridge matrix. Therefore, in this dye-sensitized solar cell, by using a solid electrolyte 25 consisting of a gel electrolyte or a completely solid electrolyte for such an electrolyte layer, the electrolyte layer caused by liquid leakage or volatilization caused when an electrolyte is used is used. Thus, a dye-sensitized solar cell with excellent cell characteristics and reliability has been realized.
  • the unsaturated double bond of the first compound is preferably, iS—unsaturated carbonyl group, a, iS—unsaturated sulfonyl group, a, —unsaturated nitrile group, and among them, ⁇ , / 3-unsaturated carbonyl groups are more preferred. It is preferable that both the first compound and the second compound have ether, ester, carbonate, alkyl, perfluorocarbon, nitrile, tertiary amine and the like in the main chain and side chain.
  • the number of unsaturated double bonds in the first compound is preferably 2 or more, but when the number of nucleophilic groups having active hydrogen in the second compound is 2, Three or more unsaturated double bonds are required.
  • the number of active hydrogen-containing nucleophilic groups in the second compound is preferably two or more, but when the number of unsaturated double bonds in the first compound is two, At least three nucleophilic groups having active hydrogen are required.
  • the gel electrolyte 25 is a gel electrolyte
  • the gel electrolyte is composed of an electrolyte composition containing a solvent and the crosslinked matrix, and the proportion of the crosslinked matrix in the gel electrolyte is 3 wt% to 5 wt%. O wt%.
  • Solvents constituting the electrolyte composition include water, alcohols, ethers, and esters.
  • the present invention is not limited to these, and they can be used alone or as a mixture of two or more. Among these, a nonprotonic nonaqueous solvent is more preferable.
  • the ratio of the electrolyte composition in the gel electrolyte is preferably 50 wt% to 97 wt%, more preferably 80 wt% to 95 wt%.
  • the electrolyte used in the gel electrolyte other combinations of I 2 and a metal iodide or an organic ® combination of ⁇ iodide, B r 2 and a metal bromide or an organic bromide, Fueroshian salt / Fuerishian salt and Hue spout / Metal complexes such as ferricinium ions, sodium polysulfide, alkyl compounds such as alkylthiol Z-alkyl disulfides, piologen dyes, hydroquinone Z quinone, and the like can be used.
  • Examples of the cation of the metal compound include Li, Na, K, Mg, Ca, and Cs, and examples of the cation of the organic compound include tetraalkylammonium.
  • Preferred are quaternary ammonium compounds such as compounds, pyridiniums and imidazoliums.
  • the present invention is not limited thereto, and these can be used alone or in combination of two or more.
  • I 2 and L i I or imidazolium ® over die de like electrolyte which combines quaternary en Moniumu compounds of are preferred.
  • the concentration of the electrolyte salt is preferably 0.05 M to 5 M, more preferably 0.2 M to 1 M, based on the solvent.
  • 1 2 Ya 8 2 concentration is preferably from 0. 0 0 0 5 1 M, more preferably from 0. 0 0 1 ⁇ 0. 1 ⁇ .
  • various additives such as 4-tert-butylpyridine and carboxylic acid can be added for the purpose of improving the open-circuit voltage and the short-circuit current.
  • the completely solid electrolyte 25 is composed of the above-mentioned crosslinked matrix containing iodine redox.
  • Electrolyte a combination of I 2 and a metal iodide or an organic iodide, B r 2 and other combinations of metal bromide or an organic bromide, Fuweroshi 7 emissions salt Z Fuerishian salt and Hue spout / Hue Rishi Niu-ion such as Metal compounds, sodium polysulfide, alkyl compounds such as alkylthiol alkyl disulfides, piologen dyes, hydroquinone / quinone, and the like can be used.
  • Examples of the cation of the metal compound include Li, Na, K, Mg, 'Ca, and Cs.
  • Examples of the cation of the organic compound include quaternary compounds such as tetraalkylammoniums, pyridiniums, and imidazolymes.
  • Ammonium compounds are suitable, but not limited thereto, and they can be used alone or as a mixture of two or more. Among them, 1 2 and L i I or imidazo Riu Muyo over die de combined electrolyte assembled quaternary Anmoniumu compounds of the like.
  • the concentration of the electrolyte salt is preferably from 0.05 M to 5 M, more preferably from 0.2 M to 1 M, based on the monomer. Ma
  • the concentration of I 2 or Br 2 is preferably 0.005 M to 1 M, and more preferably 0.001 M to 0.1 M.
  • the solid electrolyte 25 configured as described above is made of a gel electrolyte or a completely solid electrolyte, it is a highly reliable electrolyte with no leakage of the electrolyte and no deterioration in characteristics due to volatilization of the electrolyte. .
  • the matrix polymer of the solid electrolyte 25 is a polymer obtained by the Michael addition reaction of the first compound and the second compound described above, and is chemically cross-linked. Excellent in properties and durability.
  • the solid electrolyte 25 comes into contact with the solid electrolyte forming surface, that is, the electrode surface in a fluid state before polymerization, and then polymerizes, so that the electrolyte is contained in the pores of the electrode surface. Since it is sufficiently infiltrated and the state of chemical bonding at the electrochemical interface between the solid electrolyte 25 and the electrode surface is improved, it has good conductive properties.
  • the solid electrolyte 25 is formed by polymerizing the first compound and the second compound by the Michael addition reaction, it is not necessary to use heat or actinic rays during the polymerization. Therefore, an electrolyte having good conductive properties is realized without deterioration of the electrolyte composition due to heat or actinic rays at the time of formation, and the manufacturing process is simple and the productivity is excellent.
  • the solid electrolyte 25 is formed by the Michael addition reaction and is not based on the radical polymerization method, the solid electrolyte 25 can be easily prepared even in a case where iodine acts as a polymerization inhibitor in the electrolyte composition in the radical polymerization method. It can be formed in situ in a battery element, and thus is suitable for a photoelectric conversion element or the like using an iodine redox pair.
  • the dye-sensitized solar cell 21 as described above is manufactured as follows. Can be
  • a transparent electrode 3 is formed on one main surface of a transparent substrate 2, and a semiconductor layer 4 supporting a dye is formed on the transparent electrode 3 to form a semiconductor electrode. Further, a transparent electrode 7 is formed on one main surface of a transparent substrate 8, and a platinum layer 6 treated with platinum chloride is formed on the transparent electrode 7. Then, the semiconductor layer 4 supporting the dye and the platinum layer 6 face each other, and the side surfaces of the transparent substrate 2 and the transparent substrate 7 are sealed so that the semiconductor electrode and the counter electrode do not contact each other.
  • the distance between the semiconductor electrode and the counter electrode there is no particular limitation on the distance between the semiconductor electrode and the counter electrode, but it is usually lim to l01: 1, more preferably 1; m to 30 m. If the distance between the electrodes is too long, the photocurrent will decrease due to the decrease in conductivity.
  • the sealing method a material having light resistance, insulation, and moisture resistance is preferable.
  • a material having light resistance, insulation, and moisture resistance is preferable.
  • epoxy resin, ultraviolet curing resin, acrylic adhesive, ethylene vinyl acetate (EVA), ceramic, heat A fusion film or the like can be used.
  • the photoelectric conversion element of the present invention requires an injection port for injecting the solution before gelation, but the location of the injection port is not on the semiconductor layer 4 carrying the dye and the counter electrode in a portion facing the semiconductor layer 4. Is not particularly limited and can be provided at any location.
  • a mixed solution to be a precursor of the gel electrolyte 25 is prepared.
  • a first compound having two or more unsaturated double bonds is dissolved in an electrolyte solution that is an electrolyte composition.
  • the second compound having two or more nucleophilic groups having active hydrogen is dissolved. Since the nucleophilic group having active hydrogen of the second compound reacts with carbonic esters and lactones to inactivate them, esters, carbonates and lactones are used as a solvent constituting the electrolytic solution. In such a case, it is necessary to dissolve the first compound first and then dissolve the second compound.
  • the method of injecting the mixed solution is not particularly limited, but after completely dissolving these compounds, the dye-sensitized solar cell 21 is sealed in advance and the inlet of the mixed solution is opened.
  • the preferred method is to do so. In this case, it is convenient to drop several drops of the mixed solution into the injection port and inject the solution by capillary action. Further, if necessary, the mixed solution can be injected under reduced pressure. After the mixed solution is completely injected, remove the mixed solution before gelation remaining in the inlet, and seal the inlet.
  • the sealing method There is no particular limitation on the sealing method, and if necessary, the glass plate can be sealed with a sealing agent.
  • a first compound having two or more unsaturated double bonds and a second compound having two or more nucleophilic groups having active hydrogen It is preferable to allow the mixture to stand until polymerization by the Michael addition reaction with the above compound is completed.
  • the standing time There is no particular limitation on the standing time, but usually, the time required for the precursor solution introduced into the dye-sensitized solar cell 21 to completely disappear and the gelation to be completed is 1 minute to It is about 8 hours. This time may vary depending on the conditions such as the selection of the first compound, the second compound, the selection of the electrolyte, and the selection of the solvent.
  • the temperature of the atmosphere in which it is left to stand but it is usually O to 100 ° C, and it is set to 0 ° C to 60 ° C to suppress the influence on the dye and electrolyte. Is preferred.
  • the dye-sensitized solar cell 21 configured as described above includes the solid electrolyte 25 described above, there is no leakage of the electrolyte solution, no reduction in characteristics due to volatilization of the electrolyte solution, etc., and excellent reliability. Dye-sensitized solar cell is realized.
  • the matrix polymer of the solid electrolyte 25 is formed of a polymer obtained by a Michael addition reaction of the first compound and the second compound as described above, and is chemically crosslinked. Therefore, the solid electrolyte 25 is not liquefied by heat, and a dye-sensitized solar cell having excellent mechanical properties and durability is realized.
  • the solid electrolyte 25 is introduced into the dye-sensitized solar cell in a fluid state before polymerization, and then formed by polymerization, the electrode surface The inside of the pores is sufficiently impregnated with the electrolyte, and the adhesion between the semiconductor fine particles of the semiconductor layer 4 and the platinum layer 6 as the counter electrode and the solid electrolyte 25 can be increased. 4 and the solid electrolyte 25 can be sufficiently ensured, so that the electrochemical interface at the electrochemical interface between the solid electrolyte 25 and the electrode surface is good, and good photoelectric conversion characteristics are obtained. Provided dye-sensitized solar cell is realized.
  • the solid electrolyte 25 is polymerized by the Michael addition reaction as described above, the use of heat or active light is unnecessary. Therefore, since the electrolyte composition does not deteriorate due to the use of heat or actinic rays during the formation of the solid electrolyte, a photoelectric conversion element having good photoelectric conversion characteristics has been realized, and the manufacturing process is simple and the production is simple. Excellent in nature.
  • the solid electrolyte 25 is formed by a Michael addition reaction and is not based on the radical polymerization method, in the radical polymerization method, iodine acting as a polymerization inhibitor is converted into an electrolyte composition.
  • the solid electrolyte 25 can be easily formed even in the case where the solid electrolyte 25 is included, and the solid electrolyte 25 can be formed in the battery element by in-stu. Therefore, according to the dye-sensitized solar cell 21, good photoelectric conversion It is possible to easily and reliably construct a dye-sensitized solar cell having exchange characteristics.
  • an ionic liquid that is, a molten salt is used in place of the electrolyte composition containing a solvent.
  • a gel electrolyte having no vapor pressure is formed. Can also.
  • FIG. 4 is a cross-sectional view illustrating a configuration of another dye-sensitized solar cell configured by applying the present invention.
  • the dye-sensitized solar cell 31 includes a transparent substrate 2, a transparent electrode 3, a semiconductor layer 4, a solid electrolyte 35, a platinum chloride-treated platinum layer 6, a transparent electrode 7, and a transparent substrate 8. And is provided.
  • the same members as those of the dye-sensitized solar cell 1 described above are denoted by the same reference numerals as in FIG. 1, and detailed description is omitted.
  • the solid electrolyte 35 is composed of a gel electrolyte serving as a carrier transfer layer, and includes a first compound having two or more unsaturated double bonds and a second compound having two or more nucleophilic groups having active hydrogen. The compound is polymerized by a Michael addition reaction, and the polymer is used as a crosslinked matrix.
  • the solid electrolyte 35 is composed of an ionic liquid containing a redox pair and 3 to 50 wt% of the crosslinked matrix.
  • the unsaturated double bond of the first compound is represented by the following formula: PC Ranko 62
  • both the first compound and the second compound have ether, ester, carbonate, alkyl, perfluorocarbon, nitrile, tertiary amine and the like in the main chain and side chain.
  • the number of P is preferably two or more, but when the number of nucleophilic groups having active hydrogen in the second compound is two, the number of unsaturated double bonds in the first compound is three or more. is necessary.
  • the number of active hydrogen-containing nucleophilic groups in the second compound is preferably two or more, but when the number of unsaturated double bonds in the first compound is two, At least three nucleophilic groups having active hydrogen are required.
  • compounds having different skeletons may be used alone or in combination of two or more.
  • the ionic liquid examples include a pyridinium salt, an imidazolium salt, a triazolium salt, and the like. However, the ionic liquid is not limited thereto, and these can be used alone or in combination of two or more.
  • the ionic liquid preferably has a melting point of 100 ° C. or lower, more preferably 80 ° C. or lower, and particularly preferably 60 ° C. or lower.
  • the ratio of the ionic liquid in the gel electrolyte is preferably 50 wt% to 97 wt%, more preferably 80 wt% to 95 wt%.
  • the redox couple used in the gel electrolyte of the present invention is a combination of 12 and iodide of an ionic liquid, a combination of Br and a bromide of an ionic liquid. And the like, and particularly preferred is a combination of I 2 and an ionic liquid.
  • the concentration of the redox species is preferably from 0.1 wt% to 20 wt%, more preferably from 0.2 wt% to 5 wt%, based on the whole electrolyte.
  • anionic liquids with anions other than those described above can be used.
  • halogen ions such as C 1 _ and Br—, NSC—, BF 4 —, PF 6 —, and Cl 4 (CF 3 S 0 2 ) 2 N—, (CF 3 CF 2 S 0 2 ) 2 N—, CF 3 S 03-, CF 3 C ⁇ , P h 4 B—, (CF 3 S ⁇ 2) 3 C primary, include F (HF) n or the like, among the (CF 3 S_ ⁇ 2) 2 n-, or BF 4 - are preferable.
  • the redox pair may be a combination of a metal iodide or an organic iodide, a combination of Br 2 and a metal bromide or an organic bromide, or a phenocyanate Z phenocyanate or a phenocyanine ion.
  • Metal complexes such as sodium sulfide, alkyl compounds such as alkyl thiol monoalkyl disulfide, piologen dyes, and hydroquinone Z quinone.
  • Examples of the cation of the metal compound include Li, Na, K, Mg, Ca, and Cs.
  • Examples of the cation of the organic compound include quaternary ammonium such as tetraalkylammoniums, pyridiniums, and imidazoliums.
  • Compounds are suitable, but not limited thereto, and they can be used alone or as a mixture of two or more. Among them, 1 2 and Imidazoriumuyo electrolyte which combines quaternary Anmoniumu compounds such one die de are preferred.
  • the concentration of the electrolyte salt is preferably from 0.05 M to 5 M, more preferably from 0.2 M to 1 M, with respect to the ionic liquid.
  • the concentration of I 2 or Br 2 is preferably from 0.005 M to 1 M, more preferably from 0.001 M to 0.1 M.
  • 4-tert- Various additives such as butyl pyridine and carboxylic acid can also be added. Since the solid electrolyte 35 configured as described above is made of a gel electrolyte, the solid electrolyte 35 is a highly reliable electrolyte without any leakage of the electrolyte and no deterioration in characteristics due to volatilization of the electrolyte.
  • the matrix polymer of the solid electrolyte 35 is a polymer obtained by the Michael addition reaction of the first compound and the second compound described above and is chemically crosslinked, so that it does not liquefy due to heat, Excellent in properties and durability.
  • the solid electrolyte 35 comes into contact with a solid electrolyte forming surface, for example, an electrode surface in a state before polymerization having fluidity, and then polymerizes, so that the electrolyte is impregnated into pores on the electrode surface.
  • a solid electrolyte forming surface for example, an electrode surface in a state before polymerization having fluidity, and then polymerizes, so that the electrolyte is impregnated into pores on the electrode surface.
  • a solid electrolyte forming surface for example, an electrode surface in a state before polymerization having fluidity
  • the solid electrolyte 35 is formed by polymerizing the first compound and the second compound by the Michael addition reaction, it is not necessary to use heat or actinic rays for the polymerization. Therefore, an electrolyte having good conductive properties is realized without deterioration of the electrolyte composition due to heat or actinic rays at the time of formation, and the manufacturing process is simple and the productivity is excellent.
  • the solid electrolyte 35 is formed by the Michael addition reaction and is not based on the radical polymerization method, it can be easily prepared even in a case where iodine acts as a polymerization inhibitor in the electrolyte composition in the radical polymerization method. It can be formed in situ in a battery element, and thus is suitable for a photoelectric conversion element or the like using an iodine redox pair.
  • the dye-sensitized solar cell 31 as described above can be manufactured as follows. First, a transparent electrode 3 is formed on one main surface of a transparent substrate 2, and a semiconductor layer 4 supporting a dye is formed on the transparent electrode 3 to form a semiconductor electrode. Further, a transparent electrode 7 is formed on one main surface of a transparent substrate 8, and a platinum layer 6 treated with platinum chloride is formed on the transparent electrode 7. Then, the semiconductor layer 4 supporting the dye and the platinum layer 6 face each other, and the side surfaces of the transparent substrate 2 and the transparent substrate 7 are sealed so that the semiconductor electrode and the counter electrode do not contact each other. At this time, the distance between the semiconductor electrode and the counter electrode is not particularly limited, but is usually ⁇ ⁇ ! 1100 ”m, and more preferably lm330 m. If the distance between the electrodes is too long, the photocurrent will decrease due to a decrease in conductivity.
  • the sealing method a material having light resistance, insulation, and moisture resistance is preferable.
  • a material having light resistance, insulation, and moisture resistance is preferable.
  • epoxy resin, ultraviolet curing resin, acrylic adhesive, ethylene vinyl acetate (EVA), ceramic, heat A fusion film or the like can be used.
  • the photoelectric conversion element of the present invention requires an injection port for injecting the solution before gelation.
  • the injection port is The location is not particularly limited, and can be provided at any location.
  • a mixed solution to be a precursor of the gel electrolyte is prepared.
  • a first compound having two or more unsaturated double bonds is dissolved in an ionic liquid containing a redox pair.
  • a second compound having two or more nucleophilic groups having active hydrogen is dissolved to prepare a mixed solution before gelation.
  • the order of dissolution is not particularly limited. However, if the first compound and the second compound are directly mixed, the reaction may occur rapidly and solidify as it is, which is not preferable.
  • the mixed solution is injected into the dye-sensitized solar cell 31 assembled above.
  • the method of injecting the mixed solution but after completely dissolving these compounds, the dye ⁇ ⁇ ⁇ ⁇ It is preferable to inject the liquid into the positive battery 31. In this case, it is convenient to drop several drops of the mixed solution into the injection port and inject the solution by capillary action.
  • the mixed solution can be injected under reduced pressure. After the mixed solution is completely injected, remove the mixed solution before gelation remaining in the injection port, and seal the injection port.
  • the sealing method and if necessary, the glass plate can be sealed with a sealing agent.
  • a first compound having two or more unsaturated double bonds and a second compound having two or more nucleophilic groups having active hydrogen It is preferable to allow the mixture to stand until polymerization by the Michael addition reaction with the above compound is completed.
  • the time for standing There is no particular limitation on the time for standing, but usually, the time until the fluidity of the mixed solution introduced into the dye-sensitized solar cell 31 completely disappears and gelation is completed is 1 minute to 48 About an hour. Note that this time may vary depending on various conditions such as selection of the first compound, the second compound, and selection of the ionic liquid.
  • the ambient temperature at which the sample is left to stand but it is usually 0: to 100 ° C, and should be 0 ° C to 60 ° C to suppress the influence on the dye and electrolyte. Is preferred.
  • the dye-sensitized solar cell 31 can be manufactured. Since the dye-sensitized solar cell 31 configured as described above includes the solid electrolyte 35 described above, there is no leakage of the electrolyte solution, no reduction in characteristics due to volatilization of the electrolyte solution, etc., and excellent reliability. Dye-sensitized solar cell is realized.
  • the matrix polymer of the solid electrolyte 35 is formed of a polymer obtained by a Michael addition reaction of the first compound and the second compound as described above, and is chemically crosslinked. Therefore, the solid electrolyte 35 is not liquefied by heat, and a dye-sensitized solar cell excellent in mechanical properties and durability is realized.
  • a solid electrolyte When a solid electrolyte is used in a dye-sensitized solar cell, When an electrolyte is formed and the solid electrolyte is brought into close contact with the semiconductor layer to form a dye-sensitized solar cell, the semiconductor layer and the solid electrolyte are already in contact with each other in shape, that is, those having a solidified surface shape. Therefore, the adhesion between the semiconductor layer and the solid electrolyte is not good, and therefore, the contact between the semiconductor layer and the solid electrolyte becomes insufficient, which causes a problem that the photoelectric conversion efficiency is reduced.
  • the solid electrolyte 35 is introduced into the dye-sensitized solar cell in a fluid state before the polymerization, and is then formed by polymerization.
  • the inside of the pores is sufficiently impregnated with the electrolyte, and the adhesion between the semiconductor fine particles of the semiconductor layer 4 and the platinum layer 6 as the counter electrode and the solid electrolyte 35 can be increased. 4 and the solid electrolyte 35 can be sufficiently ensured, so that the electrochemical interface at the electrochemical interface between the solid electrolyte 35 and the electrode surface is good, and good photoelectric conversion characteristics are obtained.
  • Provided dye-sensitized solar cell is realized.
  • the solid electrolyte 35 is formed by polymerization by the Michael addition reaction as described above, the use of heat or active light is unnecessary. Therefore, since the electrolyte composition does not deteriorate due to the use of heat or actinic rays during the formation of the solid electrolyte, a photoelectric conversion element having good photoelectric conversion characteristics has been realized, and the manufacturing process is simple and the production is simple. Excellent in nature.
  • the solid electrolyte 35 is formed by a Michael addition reaction and is not based on the radical polymerization method, iodine acts as a polymerization inhibitor in the radical polymerization method. In this case, the solid electrolyte 35 can be easily formed, and the solid electrolyte 35 can be formed in situ in the battery element. Therefore, according to the dye-sensitized solar cell 31, a dye-sensitized solar cell having good photoelectric conversion characteristics can be simply and reliably configured. Monkey
  • photoelectric conversion element according to the present invention is not limited to the above configuration, and can be manufactured in various shapes depending on the application.
  • Example 1 a dye-sensitized solar cell element was produced as a photoelectric conversion element according to the present invention as follows. First, a TiO 2 paste was prepared. The production of the 1st and 2nd tests was performed by referring to “Latest technology of dye-sensitized solar cells” (CMC). First, 125 ml of titanium isopropoxide was slowly added dropwise to a 751 ml aqueous 0.1 M nitric acid solution at room temperature with stirring. After the completion of the dropwise addition, the mixture was transferred to a thermostat at 80 ° C. and stirred for 8 hours to obtain a cloudy translucent sol solution.
  • CMC dye-sensitized solar cells
  • sol solution was allowed to cool to room temperature, filtered through a glass filter, and then reduced to 700 ml.
  • the obtained sol solution was transferred to an autoclave, subjected to a hydrothermal treatment at 220 ° C. for 12 hours, and then subjected to a dispersion treatment by ultrasonic treatment for 1 hour.
  • the solution was then concentrated 4 0 ° C by Ebapore evening scratch, the content of T i ⁇ 2 was adjusted to 1 1 ⁇ t%. Then, the molecular weight to the concentrated sol dissolved solution was added 5 00000 Polyethylene oxa Lee de of (PEO), by homogeneously mixing to 'Rukoto in Yu star ball mill, a T i ⁇ 2 pace preparative thickened Obtained.
  • PEO Polyethylene oxa Lee de of
  • T i ⁇ 2 Bae one strike is sheet resistance of the transparent electrode 1 0 Omega Zeta fluorine doped conductive glass substrate a mouth, 1 cm X 1 was applied by screen printing the size of the cm, 4 5 0 ° C to 3 and held for 30 minutes conductive to T i ⁇ 2 A semiconductor layer was formed by sintering on the conductive glass.
  • the semiconductor layer of the semiconductor electrode prepared as described above is opposed to the platinum surface of the counter electrode, and the dye is obtained by sealing with a 20-zm-thick heat-sealing film so that the two electrodes do not come into contact with each other.
  • a sensitized solar cell element was constructed. Also, 0.2 g of lithium iodide (LiI), 1 g of pill-pill, and 3 g of a solvent obtained by mixing ethylene force and propylene force in a weight ratio of 1: 1 were added. —Dimethylimidazolium iodide 0.479 g, iodine (I 2 ) 0 ⁇ 38 1 g, and 4-tert-butylpyridine 0.2 g A liquid was prepared.
  • the dye-sensitized solar cell element was allowed to stand at a temperature of 80 ° C. for 30 minutes, so that the dye-sensitized solar cell element provided with a gel electrolyte in which the electrolyte composition was gelled. Got a child.
  • a dye-sensitized solar cell was produced in the same manner as in Example 1 except that polyoxyethylene pentaerythritol (molecular weight: 160,000) was used as the second compound.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 1, except that hexamethylene diisocyanate was used as the first compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 1 except that isophorone diisocyanate was used as the first compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 1 except that dariserin was used as the second compound and no catalyst was added.
  • a dye-sensitized solar cell was fabricated in the same manner as in Example 1, except that the first compound, the second compound, and the catalyst were not mixed with the electrolyte solution as the electrolyte composition, and the electrolyte solution was used as the electrolyte layer. did.
  • Polyethylene glycol triacrylate is mixed at 6 wt% with respect to the electrolytic solution, and tert-butyl peroxypivalate as a radical polymerization initiator is mixed at 0.15 wt% to prepare a mixed solution. After injecting the combined solution, the mixture was allowed to stand at 6 ° C. for 1 hour, and a dye-sensitized solar cell was produced in the same manner as in Example 1.
  • Polyethylene glycol diacrylate was mixed to the electrolyte at 6 wt%, and tert-butylpropyl pivalate as a radical polymerization initiator was mixed at 0.15 wt% to prepare a mixed solution.
  • a dye-sensitized solar cell was produced in the same manner as in Example 1 except that the mixed solution was poured and then left at 60 ° C. for 1 hour.
  • Example 2 After a mixed solution was prepared in the same manner as in Example 1, several drops of the mixed solution were dropped on a T i ⁇ 2 film as a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution. After standing for a time, a film-like gel electrolyte layer was formed. After the gelation, the PET film was removed, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film, except that the dye-sensitized solar cell was fabricated in the same manner as in Example 1. Produced.
  • PET polyethylene terephthalate
  • Example 3 After preparing a mixed solution in the same manner as in Example 3, several drops of the mixed solution were dropped on a Ti ⁇ 2 film as a semiconductor layer, a polyethylene terephthalate (PET) film was put on top of the mixed solution, and left for 12 hours. As a result, a film-like gel electrolyte layer was formed. After the gelation, the PET film was removed, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film, to produce a dye-sensitized solar cell in the same manner as in Example 3. did.
  • PET polyethylene terephthalate
  • Example 4 was prepared in the same manner as in the mixed solution, a few drops of the mixed solution in the semiconductor layer der Ru T i ⁇ 2 film, covered with a polyethylene terephthalate evening rate (PET) film thereon, 12 hours The film was left to form a film-like gel electrolyte layer. After the gelation, the PET film was removed, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film, to produce a dye-sensitized solar cell in the same manner as in Example 4. did.
  • PET polyethylene terephthalate evening rate
  • PET polyethylene glycol
  • the film was covered and left for 12 hours to form a film-like gel electrolyte layer. After the gelation, the PET film was removed, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film, to produce a dye-sensitized solar cell in the same manner as in Example 5. did.
  • Table 1 shows the preparation conditions of the mixed solution in each of the examples and comparative examples prepared above.
  • the dye-sensitized solar cells of Examples 1 to 5 and Comparative Examples 1 to 8 manufactured as described above were evaluated for photoelectric conversion efficiency.
  • the photoelectric conversion efficiency was measured as follows. Measurement of photoelectric conversion efficiency The measurement of photoelectric conversion efficiency was performed by applying a nip clip to the fluorine-doped conductive glass substrate on the semiconductor electrode side and the fluorine-doped conductive glass substrate on the counter electrode side in each dye-sensitized solar cell. Connect and color Motozo sensitized solar cell pseudo sunlight (AM I. 5, 1 0 O mW / cm 2) The results of performing by measuring at the irradiation shines with the current generated current voltage measuring apparatus Table 2 Show.
  • Table 2 shows Comparative Examples 2 and 3 using the conventional radical polymerization method. It can be seen that the electrolyte composition was not gelled in situ in the dye-sensitized solar cell device. On the other hand, in Examples 1 to 5 in which a first compound having two or more isocyanate groups and a second compound having two or more nucleophilic groups having active hydrogen were polymerized by a polyaddition reaction. It can be seen that the electrolyte composition was gelled in-situ in the dye-sensitized solar cell element, and that a gel electrolyte was obtained.
  • the electrolyte composition is dye-sensitized. It can be seen that gelation can be performed in-situ in the solar cell element, and a gel electrolyte can be obtained.
  • the dye-sensitized solar cell including the gel electrolyte to which the present invention is applied is a dye-sensitized solar cell configured using an electrolyte.
  • the decrease in photoelectric conversion efficiency was small, indicating good photoelectric conversion efficiency, and it can be said that an excellent dye-sensitized solar cell has been realized.
  • the first compound having two or more isocyanate groups and the second compound having two or more nucleophilic groups having active hydrogen are polymerized by a polyaddition reaction to form the first compound on the semiconductor layer in advance.
  • Comparative Examples 4 to 8 in which a gel electrolyte was formed and a counter electrode was superposed on the gel electrolyte to form a dye-sensitized solar cell were used. It can be seen that the photoelectric conversion efficiency is significantly lower than that of the configured dye-sensitized solar cell. This is probably because the electrochemical interface between the gel electrolyte formed by gelling in advance and the electrode surface has a poor chemical bonding state, and the resistance has increased.
  • Example 5 even when compared with the dye-sensitized solar cell constituted by using the electrolytic solution, the decrease in photoelectric conversion efficiency was small, and it can be seen that good photoelectric conversion efficiency was obtained. This is thought to be because the gelling of the mixed solution in contact with the electrode surface improves the chemical bonding state of the electrochemical interface between the gel electrolyte and the electrode surface, and reduces the resistance. .
  • the first compound having two or more isocyanate groups and the second compound having two or more nucleophilic groups having active hydrogen are polymerized by a polyaddition reaction in the dye-sensitized solar cell element.
  • Example 6 a dye-sensitized solar cell was produced in the same manner as in Example 1, except that the mixed solution was prepared as follows.
  • tolylene diisocyanate was mixed as a first compound having two or more isocyanate groups.
  • the mixing ratio was 1: 1 in molar ratio between the isocyanate group and the nucleophilic group having active hydrogen.
  • a mixed solution was prepared.
  • a dye-sensitized solar cell was produced in the same manner as in Example 6, except that polyoxyethylene pentaerythritol (molecular weight: 160,000) was used as the second compound.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 6, except that hexamethylene diisocyanate was used as the first compound.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 6, except that isophorone diisocyanate was used as the first compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 6, except that dariserin was used as the second compound and no catalyst was added.
  • Example 6 Same as Example 6 except that polyethylene glycol triacrylate was used, 0.15 wt% of tert-butylvaloxypivalate was mixed as a radical polymerization initiator, and the mixture was injected and left at 60 ° C for 1 hour. Thus, a dye-sensitized solar cell was produced.
  • Example 6 After preparing the same mixed solution as in Example 6, the mixture solution few drops on the semiconductor layer der Ru T i ⁇ 2 film, covered with a polyethylene terephthalate (PET) film thereon, allowed to stand for 1 2 hour As a result, a film-like complete solid electrolyte was formed. After the solidification, the PET film was removed, the counter electrode was overlaid on the solid electrolyte, and sealed with a heat-sealing film to produce a dye-sensitized solar cell in the same manner as in Example 6. did.
  • PET polyethylene terephthalate
  • PET polyethylene glycol
  • the film was covered and allowed to stand for 12 hours to form a film-like complete solid electrolyte. After the solidification, the PET film was removed, the counter electrode was overlaid on the complete solid electrolyte, and sealed with a heat-sealing film to produce a dye-sensitized solar cell in the same manner as in Example 7. did.
  • Example 8 After preparing a mixed solution in the same manner as in Example 8, several drops of the mixed solution were dropped on a Ti ⁇ 2 film as a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution. After standing for a period of time, a film-like complete solid electrolyte was formed. After the solidification, the PET film was removed, the counter electrode was superimposed on the complete solid electrolyte, and sealed with a heat-sealed film to produce a dye-sensitized solar cell in the same manner as in Example 8. did.
  • PET polyethylene terephthalate
  • PET film was covered and left for 12 hours to form a film-like complete solid electrolyte. After the solidification, the PET film was removed, the counter electrode was overlaid on the complete solid electrolyte, and sealed with a heat-sealing film, to produce a dye-sensitized solar cell in the same manner as in Example 9. .
  • Example 10 After a mixed solution was prepared in the same manner as in Example 10, several drops of the mixed solution were dropped on a Ti 2 film, which is a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution. After standing for a time, a film-like complete solid electrolyte was formed. After the solidification, the PET film was removed, the counter electrode was superimposed on the complete solid electrolyte, and sealed with a heat-sealing film, to produce a dye-sensitized solar cell in the same manner as in Example 10. .
  • PET polyethylene terephthalate
  • Table 3 shows the preparation conditions of the mixed solution in each of the examples and comparative examples prepared above.
  • Table 4 shows that in Comparative Examples 9 and 10 using the conventional radical polymerization method, the electrolyte composition was not completely solidified in-situ in the dye-sensitized solar cell device. .
  • Examples 6 to 10 in which a first compound having two or more isocyanate groups and a second compound having two or more nucleophilic groups having active hydrogen were polymerized by a polyaddition reaction, It can be seen that the electrolyte composition was completely solidified in situ in the dye-sensitized solar cell element, and that a complete solid electrolyte was obtained.
  • the electrolyte composition can be completely solidified in situ in the dye-sensitized solar cell element, and it can be seen that a completely solid electrolyte can be obtained.
  • the first compound having two or more isocyanate groups by applying the present invention and the second compound having two or more nucleophilic groups having active hydrogen are dye-sensitized solar cells.
  • the first compound having two or more isocyanate groups and the second compound having two or more nucleophilic groups having active hydrogen are polymerized by a polyaddition reaction in the dye-sensitized solar cell element.
  • a good photoelectric conversion efficiency can be obtained. It can be said that a dye-sensitized solar cell provided with the above is feasible.
  • Example 21 a dye-sensitized solar cell was produced in the same manner as in Example 1, except that a gel electrolyte was produced by preparing a mixed solution as described below.
  • EMI 1-ethyl-3-methylimidazolym
  • TFSI 1-propyl-2.3-dimethyl-imidazolidinone imid
  • the ionic liquid containing a redox pair was prepared by dissolving 0.9 M of iodine, 30 mM of iodine (I 2 ) and 0.5 M of 4-tert-butylpyridine.
  • polyoxyethylene glycerin molecular weight: 1200
  • tolylenediisocyanate as the first compound having two or more isocyanate groups.
  • the mixed solution was prepared by mixing the salts. The mixing ratio is 1: 1 in molar ratio of isocyanate groups to nucleophilic groups having active hydrogen.
  • the total amount of polyoxyethylene glycerin and tolylene disocyanate 1 is 6 wt. %.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 21 except that polyoxyethylene pen-erythritol (molecular weight: 160,000) was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 21 except that hexamethylene diisocyanate was used as the first compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 21 except that isophorone diisocyanate was used as the first compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 21 except that glycerin was used as the second compound and no catalyst was added.
  • EMI-iodide was used as the ionic liquid, and 30 mM of iodine (I 2 ) and 0.5 M of 4-tert-butylpyridine were dissolved as redox species to prepare an ionic liquid containing a redox pair. Is the same as in Example 21. Thus, a dye-sensitized solar cell was manufactured.
  • a dye-sensitized solar cell was produced in the same manner as in Example 26, except that polyoxyethylene pentaerythritol (molecular weight: 160,000) was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 26, except that hexamethylene diisocyanate was used as the first compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 26, except that isophorone diisocyanate was used as the first compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 26, except that glycerin was used as the second compound and no catalyst was added.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 21 except that the ionic liquid was not mixed with the first compound, the second compound, and the catalyst.
  • a dye-sensitized solar cell was produced in the same manner as in Example 26, except that the ionic liquid was not mixed with the first compound, the second compound, and the catalyst.
  • Example 21 A mixed solution was prepared by mixing 6 wt% of polyethylene glycol triacrylate with the ionic liquid of 1 and 0.15 ⁇ t% of tert-butyl benzopivalate as a radical polymerization initiator. After injecting this mixed solution, a dye-sensitized solar cell was produced in the same manner as in Example 21 except that the mixture was allowed to stand at 60 ° C for 1 hour.
  • Example 2 A mixed solution of 6% by weight of polyethylene glycol diacrylate and 0.15% by weight of te1-t-butylvaloxypivalate as a radical polymerization initiator was mixed with the ionic liquid of Example 1. Was prepared, and a dye-sensitized solar cell was produced in the same manner as in Example 21 except that the mixed solution was injected and then left at 60 ° C. for 1 hour.
  • Example 26 A mixed solution was prepared by mixing 6 wt% of polyethylene glycol triacrylate and 0.15 wt% of teI-t-butylbenzoicipalate as a radical polymerization initiator with the ionic liquid of Example 6. Then, a dye-sensitized solar cell was produced in the same manner as in Example 26, except that the mixed solution was poured and then left at 60 ° C. for 1 hour.
  • Example 26 A mixed solution was prepared by mixing 6 wt% of polyethylene glycol diacrylate and 0.15 wt% of tert-butyl peroxypivalate as a radical polymerization initiator with respect to the ionic liquid of Example 6.
  • a dye-sensitized solar cell was produced in the same manner as in Example 26, except that after injecting this mixed solution, the mixture was allowed to stand at 60 ° C. for 1 hour.
  • Example 2 After preparing the mixed solution in the same manner, a few drops of the mixed solution in T i ⁇ 2 film which was the semiconductor layer, covered with a polyethylene terephthalate evening rate (PET) film thereon, 1 It was left for 2 hours to form a film-like gel electrolyte layer. After the gelation, the PET film was removed, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat-sealing film to produce a dye-sensitized solar cell in the same manner as in Example 22. did.
  • PET polyethylene terephthalate evening rate
  • Example 23 After a mixed solution was prepared in the same manner as in Example 23, a few drops of the mixed solution were dropped on a Ti 2 film, which is a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution. After standing for a time, a film-like gel electrolyte layer was formed. After the gelation, the PET film was removed, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat-sealing film to produce a dye-sensitized solar cell in the same manner as in Example 23. did.
  • PET polyethylene terephthalate
  • Example 24 After a mixed solution was prepared in the same manner as in Example 24, several drops of the mixed solution were dropped on a Ti 2 film, which is a semiconductor layer, and a polyethylene terephthalate (PET) film was put on the top of the mixed solution. It was left for 2 hours to form a film-like gel electrolyte layer. After the gelation, the PET film was removed, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat-sealing film to produce a dye-sensitized solar cell in the same manner as in Example 24. did.
  • PET polyethylene terephthalate
  • Example 25 After preparing a mixed solution in the same manner as in Example 25, several drops of the mixed solution were dropped on a Ti ⁇ 2 film, which is a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution. It was left for 2 hours to form a film-like gel electrolyte layer. Then, except that the PET film was removed after gelation, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat-sealing film. A dye-sensitized solar cell was manufactured in the same manner as in Example 25.
  • PET polyethylene terephthalate
  • Example 27 After preparing a mixed solution in the same manner as in Example 27, several drops of the mixed solution were dropped on a Ti 2 film, which is a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution. This was left for 12 hours to form a film-like gel electrolyte layer. After the gelation, the PET film was removed, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat-sealing film to produce a dye-sensitized solar cell in the same manner as in Example 27. did.
  • PET polyethylene terephthalate
  • Example 28 After a mixed solution was prepared in the same manner as in Example 28, several drops of the mixed solution were dropped on a T i ⁇ ⁇ 2 film, which is a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution. This was left for 12 hours to form a film-like gel electrolyte layer. After the gelation, the PET film was removed, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film, except that the dye-sensitized solar cell was fabricated in the same manner as in Example 28. Produced.
  • T i ⁇ ⁇ 2 film which is a semiconductor layer
  • PET polyethylene terephthalate
  • Table 5 shows the preparation conditions of the mixed solution in each of the examples and the comparative examples prepared above.
  • Ratio column 23 Po J 5 Link tricle leri-: ⁇ ⁇ 1 H ⁇ X ⁇ "Ratio 24 Bo" Encore Lucia —— lert—Fuchinore 1 , "Ratio 25 ponk”:>” Lutriak ritual ——
  • Phi Lake 32 2 4-diisotrilanylene poly; ⁇ shetylene glycerin 1200) Shibuti dilauri; ⁇ 33 33 2, 4-diisotriatrilen poly; ⁇ : ⁇ !: Chile iris) Lecibutyl tin dilauri 3 ⁇ 4 ⁇ )
  • the first compound having two or more isocyanate groups and the second compound having two or more nucleophilic groups having active hydrogens are polymerized by a polyaddition reaction, whereby ionicity including a redox pair is obtained. It can be seen that the liquid can be gelled in situ in the dye-sensitized solar cell element II, and a gel electrolyte can be obtained.
  • the dye-sensitized solar cell including the gel electrolyte to which the present invention is applied includes a redox pair.
  • the decrease in photoelectric conversion efficiency is small, showing good photoelectric conversion efficiency, indicating that an excellent dye-sensitized solar cell has been realized.
  • the first compound having two or more isocyanate groups and the second compound having two or more nucleophilic groups having active hydrogen are polymerized by a polyaddition reaction, whereby the semiconductor layer is previously formed.
  • a first compound having two or more isocyanate groups by applying the present invention and a second compound having two or more nucleophilic groups having active hydrogen are contained in a dye-sensitized solar cell element.
  • the photovoltaic cells were more photovoltaic than the dye-sensitized solar cell formed using an ionic liquid containing a redox pair. It can be seen that the reduction in conversion efficiency is small and good photoelectric conversion efficiency is obtained. This is thought to be due to the fact that the gelled state of the mixed solution in contact with the electrode surface makes the electrochemical interface between the gel electrolyte and the electrode surface good, and reduces the resistance.
  • the first compound having two or more isocyanate groups and the second compound having two or more nucleophilic groups having active hydrogen are polymerized by a polyaddition reaction in the dye-sensitized solar cell element ⁇ .
  • Example 41 a dye-sensitized solar cell was produced in the same manner as in Example 1, except that the mixed solution was prepared as follows.
  • An electrolyte solution as an electrolyte composition was prepared by dissolving 9 g, iodine (I 2 ) 0.038 1 g, and 4-tert-butylpyridine 0.2 g.
  • polyethylene glycol reatalylate (molecular weight: 300,000) is mixed, and then the nucleophilic group having active hydrogen is mixed with two.
  • a mixed solution was prepared by mixing 4,4′-trimethylene dipiperidine as the second compound having at least one compound.
  • the mixing ratio is a molar ratio of unsaturated double bonds to nucleophilic groups having active hydrogen of 1: 1.
  • the total amount of polyethylene glycol triatalylate and 4,4′-trimethylenedipyridine is relative to the electrolyte. And 6 wt%.
  • a dye-sensitized solar cell was produced in the same manner as in Example 41, except that polyethylene glycol diatalylate was used as the first compound and polyethylene dali-cold lipiperidine was used as the second compound.
  • Polyethylene glycol Lipid Peridine was used as the second compound P Leakage 62
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 41 except for the above.
  • a dye-sensitized solar cell was produced in the same manner as in Example 41 except that polyethylene glycol triamine was used as the second compound '.
  • a dye-sensitized solar cell was produced in the same manner as in Example 41, except that polyethyleneimine (molecular weight: 600) was used as the second compound. ⁇ [Comparative Example 4 1]
  • the dye-sensitized solar cell was manufactured in the same manner as in Example 41 except that the first compound and the second compound were not mixed with the electrolyte solution as the electrolyte composition, and the liquid electrolyte composition was used as the electrolyte layer. Was prepared.
  • Polyethylene glycol triacrylate was mixed as the first compound in an amount of 6 wt% with respect to the electrolyte, and tert-butyl peroxybivalate was used as a radical polymerization initiator without mixing the second compound.
  • tert-butyl peroxybivalate was used as a radical polymerization initiator without mixing the second compound.
  • polyethylene diol glycol diacrylate was mixed in an amount of 6 wt% with respect to the electrolytic solution, and tert-butyl peroxyvivate was used as a radical polymerization initiator without mixing the second compound.
  • a mixed solution was prepared by mixing 0.15 wt%, and the mixed solution was injected, and then left at 60 ° C for 1 hour, except that the dye-sensitized dye was used in the same manner as in Example 41.
  • a positive battery was manufactured.
  • Example 41 After a mixed solution was prepared in the same manner as in 1, a few drops of the mixed solution were dropped on a Ti ⁇ 2 film as a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution for 12 hours. The film was left to form a film-like gel electrolyte layer. After the gelation, the PET film was removed, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film, except that the dye-sensitized solar cell was the same as in Example 41. Was prepared.
  • PET polyethylene terephthalate
  • Example 4 2 After preparing the same mixed solution as in Example 4 2, a few drops of the mixed solution in T i ⁇ 2 film which was the semiconductor layer, covered with a polyethylene terephthalate (PET) film thereon, 12 hours The film was left to form a film-like gel electrolyte layer. Then, the PET film was removed in the same manner as in Example 42 except that the PET film was removed after gelation, the counter electrode was overlapped with the gel electrolyte layer, and sealed with a heat sealing film. Was prepared.
  • PET polyethylene terephthalate
  • Example 4 After preparing the same mixed solution as in Example 4 3, a few drops of the mixed solution in T i 0 2 film which was the semiconductor layer, covered with a polyethylene terephthalate (PET) film thereon, 12 hours The film was left to form a film-like gel electrolyte layer. After the gelation, the PET film was removed, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat-sealing film. Produced.
  • PET polyethylene terephthalate
  • Example 44 After preparing a mixed solution in the same manner as in Example 44, several drops of the mixed solution were dropped on a TiO 2 film, which is a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution for 12 hours. The film was left to form a film-like gel electrolyte layer. After gelation, the PET film was removed, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film. 62
  • PET polyethylene terephthalate
  • a dye-sensitized solar cell was produced in the same manner as in Example 44 except for 71.
  • Example 45 After preparing a mixed solution in the same manner as in Example 45, several drops of the mixed solution were dropped on a Ti ⁇ 2 film as a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on the top of the mixed solution for 12 hours. The film was left to form a film-like gel electrolyte layer. After the gelation, the PET film was removed, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat-sealing film, except that the dye-sensitized solar cell was fabricated in the same manner as in Example 45. Produced.
  • PET polyethylene terephthalate
  • Table 7 shows the preparation conditions of the mixed solution in each of the examples and comparative examples prepared above.
  • the first compound having two or more unsaturated double bonds and the second compound having two or more nucleophilic groups having active hydrogen are polymerized by a Michael addition reaction, whereby the electrolyte is It can be seen that the composition can be gelled in-situ in the dye-sensitized solar cell device, and a gel electrolyte can be obtained. .
  • the dye-sensitized solar cell including the gel electrolyte to which the present invention was applied was found to have a liquid electrolyte composition, that is, an electrolytic solution.
  • a liquid electrolyte composition that is, an electrolytic solution.
  • the first compound having two or more unsaturated double bonds and the second compound having two or more nucleophilic groups having active hydrogen are polymerized by a Michael addition reaction, whereby the Comparative Examples 44 to 48 in which a gel electrolyte was formed on the semiconductor layer and a counter electrode was superposed on the gel electrolyte to form a dye-sensitized solar cell, a gel electrolyte was obtained.
  • the photoelectric conversion efficiency is significantly lower than that of a dye-sensitized solar cell formed using a liquid electrolyte composition, that is, an electrolytic solution. This is presumably because the electrochemical interface between the gel electrolyte formed by gelling in advance and the electrode surface has a poor chemical bonding state and the resistance has increased.
  • a first compound having two or more unsaturated double bonds and a second compound having two or more nucleophilic groups having active hydrogen are contained in a dye-sensitive solar cell element.
  • the liquid electrolyte composition that is, the dye-sensitized solar cell formed using the electrolytic solution was compared with the liquid electrolyte composition. Also, it can be seen that the photoelectric conversion efficiency did not decrease much, and that a good photoelectric conversion efficiency was obtained. This is when the mixed solution is in contact with the electrode surface 03 04562
  • the gelation improves the chemical bonding state of the electrochemical interface between the gel electrolyte and the electrode surface, and reduces the resistance.
  • the first compound having two or more unsaturated double bonds and the second compound having two or more nucleophilic groups having active hydrogen in Michael in the dye-sensitized solar cell element By polymerizing by the addition reaction, it is possible to gel the electrolyte composition in situ in the dye-sensitized solar cell element to produce a gel electrolyte. By using the gel electrolyte, a good photoelectricity can be obtained. It can be said that a dye-sensitive solar cell with conversion efficiency can be realized.
  • Example 46 a dye-sensitized solar cell was produced in the same manner as in Example 41, except that the mixed solution was prepared as follows.
  • a dye-sensitized solar cell was produced in the same manner as in Example 46, except that polyethylene glycol diacrylate was used as the first compound and polyethylene glycol'tripiperidine was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 46, except that polyethylenedaricol tripididine was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 46, except that polyethylene glycol triamine was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 46, except that polyethyleneimine (molecular weight: 600) was used as the second compound.
  • Polyethylene glycol triatalylate is mixed as the first compound in an amount of 6 wt% with respect to the electrolyte composition, and tert-butyl peroxybivalate is used as a radical polymerization initiator without mixing the second compound.
  • tert-butyl peroxybivalate is used as a radical polymerization initiator without mixing the second compound.
  • Polyethylene dalicol diacrylate was mixed as the first compound in an amount of 6 wt% with respect to the electrolyte la, and tert-butyl peroxyl was used as the radical polymerization initiator without mixing the second compound. 0.15 wt% of pivalate was mixed to prepare a mixed solution, and the mixed solution was poured and then left at 60 ° C. for 1 hour to prepare a dye solution in the same manner as in Example 46. A solar cell was manufactured.
  • Example 46 After preparing a mixed solution in the same manner as in Example 46, several drops of the mixed solution were dropped on a TiO 2 film as a semiconductor layer, a polyethylene terephthalate (PET) film was put on top of the mixed solution, and left for 12 hours. Thus, a film-like complete solid electrolyte was formed. After the solidification, the PET film was removed, the counter electrode was superimposed on the complete solid electrolyte, and sealed with a heat-sealing film. Produced.
  • PET polyethylene terephthalate
  • Example 47 After preparing a mixed solution in the same manner as in Example 47, a few drops of the mixed solution were dropped on a TiO 2 film as a semiconductor layer, a polyethylene terephthalate (PET) film was put on the top of the mixed solution, and left for 12 hours. Thus, a film-like complete solid electrolyte was formed. After solidification, the PET film was removed, the counter electrode was superimposed on the complete solid electrolyte, and sealed with a heat-sealing film. did.
  • PET polyethylene terephthalate
  • Example 48 After preparing a mixed solution in the same manner as in Example 48, several drops of the mixed solution were dropped on a TiO 2 film, which is a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution, and left for 12 hours. Thus, a film-like complete solid electrolyte was formed. Then, a dye-sensitized solar cell was manufactured in the same manner as in Example 48 except that the PET film was removed after solidification, the counter electrode was superimposed on the complete solid electrolyte, and sealed with a heat-sealing film. .
  • PET polyethylene terephthalate
  • Example 49 After preparing a mixed solution in the same manner as in Example 49, several drops of the mixed solution were dropped on a TiO 2 film as a semiconductor layer, a polyethylene terephthalate (PET) film was put on top of the mixed solution, and left for 12 hours. Thus, a film-like complete solid electrolyte was formed. Then, a dye-sensitized solar cell was manufactured in the same manner as in Example 49 except that the PET film was removed after solidification, the counter electrode was overlaid on the complete solid electrolyte, and sealed with a heat-sealing film. .
  • PET polyethylene terephthalate
  • Example 50 After preparing a mixed solution in the same manner as in Example 50, several drops of the mixed solution were dropped on a TiO 2 film as a semiconductor layer, a polyethylene terephthalate (PET) film was put on the top of the mixed solution, and left for 12 hours. Thus, a film-like complete solid electrolyte was formed. And solid PC Mongolia 62
  • Example 50 After that, the PET film was removed, the counter electrode was overlaid on the complete solid electrolyte, and sealed with a heat-sealing film, to produce a dye-sensitive solar cell in the same manner as in Example 50.
  • Table 9 shows the preparation conditions of the mixed solution in each of the examples and the comparative examples prepared above.
  • Table 10 shows that in Comparative Examples 42 and 43 using the conventional radical polymerization method, the electrolyte composition was not completely solidified in situ in the dye-sensitized solar cell device.
  • a Michael addition reaction between a first compound having at least two unsaturated double bonds and a second compound having at least two nucleophilic groups having active hydrogen In Examples 46 to 50, the electrolyte composition was gelled in situ in the dye-sensitized solar cell element, and a complete solid electrolyte was obtained. I understand.
  • the first compound having two or more unsaturated double bonds and the second compound having two or more nucleophilic groups having active hydrogen are polymerized by a Michael addition reaction, whereby the electrolyte is It can be seen that the composition can be completely solidified in-situ in the dye-sensitive solar cell element, and a completely solid electrolyte can be obtained. From Table 10, it can be seen that the first compound having two or more unsaturated double bonds and the second compound having two or more nucleophilic groups having active hydrogen are dye-sensitized by applying the present invention.
  • Examples 46 to 50 in which a solid electrolyte was formed in advance on a semiconductor layer by polymerizing by a Michael addition reaction in a solar cell element to be completely solidified in situ, It can be seen that higher photoelectric conversion efficiencies were obtained as compared with Comparative Examples 51 to 55 in which the counter electrode was superposed on the electrolyte to form a dye-sensitized solar cell. This is because, in Examples 46 to 50, the electrolyte solution is completely solidified in contact with the electrode surface, and the chemical bonding state of the electrochemical interface between the completely solid electrolyte and the electrode surface is reduced. It is considered to be good and the resistance is small, so that high photoelectric conversion efficiency is obtained.
  • Experiment 6 a photoelectric conversion device including another gel electrolyte according to the present invention was examined.
  • Example 51 a dye-sensitized solar cell was produced in the same manner as in Example 1, except that a gel electrolyte was produced by preparing an ionic liquid as follows.
  • EMI 1-ethyl- 3 -methylimidazolidum
  • polyethylene glycol triatalylate (molecular weight: 300,000) is mixed, and then two or more nucleophilic groups having active hydrogen are added.
  • a mixed solution was prepared by mixing 4,4′-trimethylene dipiperidine as a second compound having the compound.
  • the mixing ratio is a molar ratio of unsaturated double bonds to nucleophilic groups having active hydrogen of 1: 1.
  • the total amount of polyethylene glycol triacrylate and 4,4,1-trimethylenedipipyridine is an ionic liquid. And 6 wt% with respect to the mixture.
  • the device was allowed to stand at room temperature for 12 hours to obtain a dye-sensitized solar cell provided with a gel electrolyte formed by gelling an ionizable liquid containing a redox couple.
  • a dye-sensitized solar cell was produced in the same manner as in Example 51, except that polyethylene dalicol diacrylate was used as the first compound and polyethylene dali konole letripiperidine was used as the second compound.
  • polyethylene dalicol diacrylate was used as the first compound
  • polyethylene dali konole letripiperidine was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 51 except that polyethylene glycol tripididine was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 51, except that polyethylene dalicol triamine was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 51, except that polyethyleneimine (molecular weight: 600) was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 56, except that polyethylene glycol diacrylate was used as the first compound, and polyethylene dalicol tripiperidine was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 56 except that polyethylenedaricol tripididine was used as the second compound.
  • a dye-sensitized solar cell was produced in the same manner as in Example 56, except that polyethylene dalicol triamine was used as the second compound.
  • a dye-sensitive solar cell was produced in the same manner as in Example 51, except that the first compound and the second compound were not mixed with the ionic liquid.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 56, except that the first compound and the second compound were not mixed with the ionic liquid. ⁇
  • Example 5 A mixed solution was prepared by mixing 6 wt% of polyethylene diol triacrylate and 0.15 wt% of tert-butyl peroxybivalate as a radical polymerization initiator with respect to the ionic liquid of 1. Then, a dye-sensitized solar cell was manufactured in the same manner as in Example 51, except that the mixed solution was poured and then left at 60 ° C. for 1 hour.
  • Example 5 6 wt of polyethylene daricol diacrylate was added to the ionic liquid of 1. /.
  • a mixed solution was prepared by mixing 0.15 wt% of tert-butyl peroxybivalate as a radical polymerization initiator, and after pouring the mixed solution, the mixture was left at 60 ° C for 1 hour.
  • a dye-sensitized solar cell was produced in the same manner as in Example 51.
  • Example 5 A mixed solution was prepared by mixing 6 wt% of polyethylene glycol triatalylate and 0.15 wt% of tert-butyl peroxypivalate as a radical polymerization initiator with respect to the ionic liquid of 6, A dye-sensitized solar cell was produced in the same manner as in Example 56, except that the mixed solution was poured and then left at 60 ° C. for 1 hour.
  • Example 56 Polyethylene glycol diacrylate was added to the ionic liquid of 6 A mixed solution was prepared by mixing 0.15 wt% of tert-butyl peroxybivalate as a radical polymerization initiator with 6 wt%, and after pouring the mixed solution, the mixture was allowed to stand at 60 ° C. for 1 hour. Except for the above, a dye-sensitized solar cell was produced in the same manner as in Example 56.
  • Example 51 After a mixed solution was prepared in the same manner as in Example 51, several drops of the mixed solution were dropped on a TiO 2 film as a semiconductor layer, and a polyethylene terephthalate (PET) film was placed on top of the mixed solution. This was left for a time to form a film-like gel-like electrolytic layer. Then, the dye-sensitized solar cell was fabricated in the same manner as in Example 51 except that the PET film was removed after gelation, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat sealing film. Produced.
  • PET polyethylene terephthalate
  • Example 5 2 After preparing the mixed solution in the same manner as in Example 5 2, a few drops of the mixed solution in T I_ ⁇ 2 film which was the semiconductor layer, covered with a polyethylene terephthalate (PET) Fi Lum thereon, 12 hours The film was left to form a film-like gel-like electrolytic layer. Then, the dye-sensitized solar cell was fabricated in the same manner as in Example 52 except that the PET film was removed after gelation, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat sealing film. Produced.
  • PET polyethylene terephthalate
  • Example 5 After preparing the mixed solution in the same manner as in Example 5 3, a few drops of the mixed solution in T I_ ⁇ 2 film which was the semiconductor layer, covered with a polyethylene terephthalate (PET) Fi Lum thereon, 12 hours The film was left to form a film-like gel-like electrolytic layer. After the gelation, the PET film was removed, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film, except that the dye-sensitized solar cell was fabricated in the same manner as in Example 53. Produced.
  • PET polyethylene terephthalate
  • Example 54 After a mixed solution was prepared in the same manner as in Example 54, the mixed solution was used as a semiconductor layer T I_ ⁇ few drops on 2 film, the upper covered with polyethylene terephthalate (PET) Fi Lum in, to form a film-like gel electrolyte layer and left for 12 hours. Then, the PET film was removed after gelling, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film in the same manner as in Example 54, except that Was prepared.
  • PET polyethylene terephthalate
  • Example 5 After preparing the mixed solution in the same manner as in Example 5 5, a few drops of the mixed solution in T I_ ⁇ 2 film which was the semiconductor layer, covered with a polyethylene terephthalate (PET) Fi Lum thereon, 12 hours The film was left to form a film-like gel-like electrolytic layer. Then, except that the PET film was removed after gelation, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat-sealing film, a dye-sensitized solar cell was produced in the same manner as in Example 55. Produced.
  • PET polyethylene terephthalate
  • Example 5 6 and after preparing a mixed solution in the same manner, a few drops of the mixed solution in T i 0 2 film which was the semiconductor layer, covered with a polyethylene terephthalate (PET) Fi Lum thereon, 12 hours The film was left to form a film-like gel-like electrolytic layer. Then, the dye-sensitive solar cell was fabricated in the same manner as in Example 56 except that the PET film was removed after gelling, the counter electrode was overlapped with the gel electrolyte layer, and sealed with a heat-sealing film. Produced.
  • PET polyethylene terephthalate
  • Example 5 7 and after the preparation of the mixed solution in the same manner, a few drops of the mixed solution in T i 0 2 film which was the semiconductor layer, covered with a polyethylene terephthalate (PET) Fi Lum thereon, 12 hours The film was left to form a film-like gel-like electrolytic layer. Then, the dye-sensitized solar cell was fabricated in the same manner as in Example 57 except that the PET film was removed after gelation, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film. Produced. n to TM
  • Example 5 After preparing the mixed solution in the same manner as in Example 5 8, a few drops of the mixed solution in T I_ ⁇ 2 film which was the semiconductor layer, covered with a polyethylene terephthalate (PET) Fi Lum thereon, 12 hours The film was left to form a film-like gel-like electrolytic layer. Then, the PET-film was removed in the same manner as in Example 58 except that the PET film was removed after the gelation, the counter electrode was overlaid on the gel electrolyte layer, and sealed with a heat-sealing film. Produced.
  • PET polyethylene terephthalate
  • Example 6 After preparing the mixed solution in the same manner as in Example 6 0, a few drops of the mixed solution in T i 0 2 film which was the semiconductor layer, covered with a polyethylene terephthalate (PET) buoy Lum thereon, 12 hours The film was left to form a film-like gel-like electrolytic layer. After the gelation, the PET film was removed, the counter electrode was superimposed on the gel electrolyte layer, and sealed with a heat-sealing film, except that the dye-sensitized solar cell was fabricated in the same manner as in Example 60. Produced.
  • PET polyethylene terephthalate
  • Table 11 shows the preparation conditions of the mixed solution in each of the examples and the comparative examples prepared above.
  • Example 6 0 was prepared, and Comparative Example 5 1 Comparative Example 6 6 dye-sensitized solar cell. Table 12 shows the results.
  • each dye-sensitized solar cell was disassembled, the internal electrolyte portion was taken out, and the presence or absence of gelation of the electrolyte was visually checked.
  • the results are shown in Table 12.
  • ⁇ indicates gelation
  • X indicates non-gelation.
  • Table 12 shows that in Comparative Examples 53 to 56 using the conventional radical polymerization method, the ionic liquid containing the reddots pair was gelled in-situ in the dye-sensitized solar cell device. It turns out that there is no.
  • Examples 51 to Example in which a first compound having two or more unsaturated double bonds and a second compound having two or more nucleophilic groups having active hydrogen were polymerized by Michael addition reaction In the case of 60, the ionic liquid containing the redox couple was gelled in situ in the dye-sensitized solar cell device II, and it was found that a gel electrolyte was obtained.
  • first compound having two or more unsaturated double bonds and the second compound having two or more nucleophilic groups having active hydrogens are polymerized by a Michael addition reaction, thereby forming a redox pair. It is possible to gel an ionic liquid containing in situ in a dye-sensitized solar cell element, and it is understood that a gel electrolyte can be obtained.
  • the dye-sensitized solar cell including the gel electrolyte to which the present invention is applied includes a redox pair.
  • the decrease in photoelectric conversion efficiency is small, showing good photoelectric conversion efficiency, indicating that an excellent dye-sensitized solar cell has been realized. .
  • the first compound having two or more unsaturated double bonds and the second compound having two or more nucleophilic groups having active hydrogen are polymerized by Michael addition reaction.
  • Form a gel electrolyte on the semiconductor layer in advance Comparative Examples 57 to 66, in which a dye-sensitized solar cell was constructed by superposing a counter electrode on the gel electrolyte, the gel electrolyte was obtained, but the ionic It can be seen that the photoelectric conversion efficiency is significantly lower than that of the dye-sensitized solar cell configured using a liquid. This is considered to be due to the poor chemical bonding state of the electrochemical interface between the gel electrolyte formed by gelation in advance and the electrode surface, and increased resistance.
  • a first compound having two or more unsaturated double bonds and a second compound having two or more nucleophilic groups having active hydrogen are dye-sensitized solar cell elements.
  • the polymer was polymerized by the Michael addition reaction in-situ and gelled in-situ, compared with the dye-sensitized solar cell constituted by using an ionic liquid containing a redox pair, Also, it can be seen that the photoelectric conversion efficiency did not decrease much, and that good photoelectric conversion efficiency was obtained. This is thought to be because the gelling of the mixed solution in contact with the electrode surface improves the chemical bonding state of the electrochemical interface between the gel electrolyte and the electrode surface and reduces the resistance. .
  • the first compound having two or more unsaturated double bonds and the second compound having two or more nucleophilic groups having active hydrogen are mixed in a dye-sensitized solar cell element by Michael.
  • Michael By polymerizing by an addition reaction, it is possible to gel an ionic liquid containing a redox pair in-situ in a dye-sensitized solar cell element to produce a gel electrolyte. It can be said that a dye-sensitized solar cell having good photoelectric conversion efficiency can be realized by using this.
  • the solid electrolyte according to the present invention is a solid electrolyte having an electrolyte composition and a matrix polymer, wherein the matrix polymer is an isocyanate.
  • the first compound having two or more nucleophilic groups and the second compound having two or more nucleophilic groups having active hydrogen are polymerized by a polyaddition reaction, and are not polymerized on the surface forming the solid electrolyte. And then polymerized.
  • another solid electrolyte according to the present invention is a solid electrolyte having an electrolyte composition and a matrix polymer, wherein the matrix polymer has a first polymer having two or more unsaturated double bonds. And a second compound having two or more nucleophilic groups having active hydrogen are polymerized by a Michael addition reaction, and contact the surface forming the solid electrolyte in a state before the polymerization, and thereafter It is a superposition.
  • the solid electrolyte according to the present invention configured as described above comes into contact with the solid electrolyte forming surface, for example, the electrode surface, in a state before the polymerization with fluidity, and then polymerizes.
  • a solid electrolyte can be formed in situ, and the state of chemical bonding at the electrochemical interface between the solid electrolyte and the electrode surface is good.
  • the electrolyte composition does not deteriorate due to heat or actinic rays during formation.
  • the matrix polymer of the solid electrolyte is a polymer obtained by a polyaddition reaction between the first compound and the second compound described above and is chemically crosslinked, so that it does not liquefy due to heat. Excellent mechanical properties and durability.
  • the photoelectric conversion element according to the present invention using the solid electrolyte includes a semiconductor layer made of semiconductor particles carrying a dye and an electrolyte layer between an electrode formed on the surface of the transparent substrate and a counter electrode.
  • the first compound and a second compound having two or more nucleophilic groups having active hydrogen are polymerized by a polyaddition reaction, and contact the surface forming a solid electrolyte in a state before polymerization, Thereafter, it is polymerized.
  • the method for manufacturing a photoelectric conversion element includes a photoelectric conversion element including a semiconductor layer made of semiconductor particles carrying a dye and an electrolyte layer between an electrode formed on the surface of a transparent substrate and a counter electrode.
  • a method for producing comprising: assembling the photoelectric conversion element, a first compound having two or more isocyanate groups, a second compound having two or more nucleophilic groups having active hydrogen, and a Redottas pair.
  • a mixed solution containing an electrolyte composition containing the first compound and the second compound is polymerized by a polyaddition reaction in the photoelectric conversion element, and solidified. The above-mentioned electrolyte layer is formed.
  • another photoelectric conversion element includes a semiconductor layer made of semiconductor particles carrying a dye and an electrolyte layer between an electrode formed on a surface of a transparent substrate and a counter electrode.
  • the electrolyte layer has a redox couple, an electrolyte composition, and a matrix polymer, and the matrix polymer has two or more unsaturated double bonds.
  • One compound and a second compound having two or more nucleophilic groups having active hydrogen are polymerized by a Michael addition reaction, and come into contact with a surface forming a solid electrolyte in a state before polymerization, Thereafter, it is polymerized.
  • the method for manufacturing a photoelectric conversion element includes a photoelectric conversion element including a semiconductor layer made of semiconductor particles carrying a dye and a solid electrolyte layer between an electrode formed on the surface of a transparent substrate and a counter electrode.
  • a method of preparing the photoelectric conversion device wherein a first compound having two or more unsaturated double bonds and a second compound having two or more nucleophilic groups having active hydrogen are provided.
  • the first compound and the second compound are polymerized by a Michael addition reaction in the photoelectric conversion element to be solidified in the photoelectric conversion element to form the solid electrolyte layer.
  • a fluid mixed solution is introduced into the photoelectric conversion device in a state before polymerization, and then polymerized to form the solid electrolyte according to the present invention. For this reason, since a solid electrolyte can be formed in the battery element using in-stu, a photoelectric conversion element having good photoelectric conversion characteristics can be simply and reliably realized.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)
  • Conductive Materials (AREA)

Abstract

La présente invention concerne un électrolyte solide très sûr qui présente de très bonnes caractéristiques de conductivité, un convertisseur photoélectrique comprenant cet électrolyte et un procédé pour produire celui-ci. Ledit électrolyte solide comprend une composition électrolytique et un polymère matriciel caractérisé en ce qu'il est produit par polymérisation à l'aide d'une réaction de polyaddition entre un premier composé présentant au moins deux groupes isocyanate et un second composé présentant au moins deux groupes nucléophiles possédant un hydrogène actif, le polymère matriciel en condition de prépolymérisation étant mis en contact avec une surface de formation d'électrolyte solide, puis étant ensuite soumis à une polymérisation.
PCT/JP2003/004562 2002-04-11 2003-04-10 Electrolyte solide, convertisseur photoelectrique et procede pour produire celui-ci WO2003085680A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP03717557A EP1494246B1 (fr) 2002-04-11 2003-04-10 Electrolyte solide, convertisseur photoelectrique et procede pour produire celui-ci
AU2003227481A AU2003227481A1 (en) 2002-04-11 2003-04-10 Solid electrolyte, photoelectric converter and process for producing the same
US10/511,012 US7880082B2 (en) 2002-04-11 2003-04-10 Solid electrolyte, photoelectric converter and process for producing the same
KR1020047016187A KR101005570B1 (ko) 2002-04-11 2003-04-10 광전변환소자의 제조방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-109427 2002-04-11
JP2002109427A JP4010170B2 (ja) 2002-04-11 2002-04-11 光電変換素子の製造方法

Publications (1)

Publication Number Publication Date
WO2003085680A1 true WO2003085680A1 (fr) 2003-10-16

Family

ID=28786580

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/004562 WO2003085680A1 (fr) 2002-04-11 2003-04-10 Electrolyte solide, convertisseur photoelectrique et procede pour produire celui-ci

Country Status (7)

Country Link
US (1) US7880082B2 (fr)
EP (1) EP1494246B1 (fr)
JP (1) JP4010170B2 (fr)
KR (1) KR101005570B1 (fr)
CN (1) CN100380530C (fr)
AU (1) AU2003227481A1 (fr)
WO (1) WO2003085680A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100567330B1 (ko) 2004-08-04 2006-04-04 한국전자통신연구원 이중구조의 염료감응 태양전지
EP1699063A1 (fr) * 2005-03-03 2006-09-06 Fuji Photo Film Co., Ltd. Semiconducteur avec une substance adsorbée

Families Citing this family (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003264556B2 (en) * 2002-09-25 2008-11-06 Dai-Ichi Kogyo Seiyaku Co., Ltd. Dye-sensitized solar cell
US20050150544A1 (en) * 2003-12-05 2005-07-14 Sharp Kabushiki Kaisha Dye-sensitized solar cell
US20060174938A1 (en) * 2005-02-04 2006-08-10 Stmicroelectronics S.R.L. Water-based electrolyte gel for dye-sensitized solar cells and manufacturing methods
US20090032105A1 (en) * 2005-04-11 2009-02-05 Nippon Kayaku Kabushiki Kaisha Electrolyte Composition for Photoelectric Converter and Photoelectric Converter Using Same
EP1926682A4 (fr) * 2005-06-21 2012-06-20 Crosslink Polymer Res Enduit décontaminant activé par signal
KR100819025B1 (ko) * 2005-12-08 2008-04-02 한국전자통신연구원 고분자 전해질 조성물, 이를 포함하는 염료감응 태양전지,및 상기 염료감응 태양전지의 제조방법
KR100880523B1 (ko) * 2005-12-30 2009-01-28 주식회사 엘지화학 공융혼합물을 포함하는 전해질을 구비한 전기변색소자
JP5007784B2 (ja) * 2006-01-30 2012-08-22 ソニー株式会社 光電変換装置
JP2007234580A (ja) * 2006-02-02 2007-09-13 Sony Corp 色素増感型光電変換装置
JP2007280906A (ja) * 2006-04-12 2007-10-25 Sony Corp 機能デバイス及びその製造方法
KR100854712B1 (ko) * 2006-10-13 2008-08-27 한국과학기술연구원 탄소소재층을 포함하는 염료감응 태양전지용 상대전극 및이의 제조방법
SG144830A1 (en) * 2007-01-18 2008-08-28 Applied Materials Inc High temperature fine grain aluminum heater
JP5224604B2 (ja) * 2007-07-25 2013-07-03 綜研化学株式会社 色素増感太陽電池
JP5023866B2 (ja) * 2007-07-27 2012-09-12 ソニー株式会社 色素増感光電変換素子およびその製造方法ならびに電子機器
JP2009075254A (ja) * 2007-09-19 2009-04-09 Fujifilm Corp 焦点検出装置及び撮影装置
JP2009099476A (ja) * 2007-10-19 2009-05-07 Sony Corp 色素増感光電変換素子およびその製造方法
JP2009110796A (ja) * 2007-10-30 2009-05-21 Sony Corp 色素増感光電変換素子モジュールおよびその製造方法ならびに電子機器
JP2009146625A (ja) * 2007-12-12 2009-07-02 Sony Corp 色素増感光電変換素子モジュールおよびその製造方法ならびに光電変換素子モジュールおよびその製造方法ならびに電子機器
JPWO2009087793A1 (ja) * 2008-01-11 2011-05-26 独立行政法人科学技術振興機構 電界効果トランジスタ、電界効果トランジスタの製造方法、中間体及び第２中間体
US20090291844A1 (en) * 2008-05-23 2009-11-26 Lumimove, Inc. Dba Crosslink Electroactivated film with immobilized peroxide activating catalyst
WO2009143314A2 (fr) * 2008-05-23 2009-11-26 Lumimove, Inc., A Missouri Corporation, Dba Crosslink Film électroactivé avec électrolyte en gel polymère
JP2010003468A (ja) * 2008-06-19 2010-01-07 Sony Corp 色素増感太陽電池およびその製造方法
JP2010010191A (ja) * 2008-06-24 2010-01-14 Sony Corp 電子装置
JP2010009769A (ja) * 2008-06-24 2010-01-14 Sony Corp 光電変換素子の製造方法
US20100108116A1 (en) * 2008-08-01 2010-05-06 University Of Washington Enhanced Dye Sensitized Solar Cells
KR100997843B1 (ko) * 2008-08-29 2010-12-01 주식회사 솔켐 전기방사법에 의해 제조된 고분자 전해질을 포함한 염료감응형 태양전지 소자 및 이의 제조방법
JP2010092762A (ja) * 2008-10-09 2010-04-22 Sony Corp 機能性デバイス及びその製造方法
BRPI0919906A2 (pt) 2008-10-29 2016-02-16 Fujifilm Corp corante, elemento de conversão fotoelétrico e célula fotoeletroquímica cada uma compreendendo o corante e o processo para produzir corante.
WO2010059498A2 (fr) * 2008-11-18 2010-05-27 Konarka Technologies, Inc. Cellule photovoltaïque sensibilisée par colorant
US20110048525A1 (en) * 2008-11-26 2011-03-03 Sony Corporation Functional device and method for producing the same
CN101447340B (zh) * 2008-12-11 2011-08-17 彩虹集团公司 用于染料敏化太阳能电池的大表面积电极制备方法
TW201024267A (en) * 2008-12-19 2010-07-01 Ind Tech Res Inst Electrolyte composition and dye-sensitized solar cell using the same
JP5444747B2 (ja) * 2009-02-17 2014-03-19 ソニー株式会社 カラー撮像素子およびその製造方法ならびに光センサーおよびその製造方法ならびに光電変換素子およびその製造方法ならびに電子機器
US8288646B2 (en) * 2009-05-06 2012-10-16 UltraSolar Technology, Inc. Pyroelectric solar technology apparatus and method
JP5428555B2 (ja) * 2009-06-08 2014-02-26 ソニー株式会社 色素増感光電変換素子の製造方法
JP5620081B2 (ja) 2009-09-28 2014-11-05 富士フイルム株式会社 光電変換素子の製造方法
JP5524557B2 (ja) 2009-09-28 2014-06-18 富士フイルム株式会社 光電変換素子の製造方法、光電変換素子、および光電気化学電池
US20110203644A1 (en) * 2010-02-22 2011-08-25 Brite Hellas Ae Quasi-solid-state photoelectrochemical solar cell formed using inkjet printing and nanocomposite organic-inorganic material
JP2011204662A (ja) * 2010-03-05 2011-10-13 Sony Corp 光電変換素子およびその製造方法ならびに電子機器
JP5621488B2 (ja) * 2010-03-17 2014-11-12 ソニー株式会社 光電変換装置
JP2011198691A (ja) * 2010-03-23 2011-10-06 Sekisui Plastics Co Ltd ゲル状イオン導電体及びその製造方法
CN102082204B (zh) * 2010-12-02 2012-10-10 上海超日(洛阳)太阳能有限公司 一种减少槽式去psg设备产生水渍的方法
CN102184978B (zh) * 2011-02-28 2013-04-17 上海师范大学 一种半导体纳米晶/量子点敏化的晶硅材料及其制备方法
CN102184979B (zh) * 2011-02-28 2013-05-01 上海师范大学 一种半导体纳米晶/量子点敏化的晶硅材料及其制备方法
JP2012227063A (ja) * 2011-04-21 2012-11-15 Dainippon Printing Co Ltd 色素増感型太陽電池素子モジュール
JP2013093176A (ja) * 2011-10-25 2013-05-16 Osaka Gas Co Ltd 電解液及び光電変換素子
EP3010054B1 (fr) * 2012-05-18 2019-02-20 Oxford University Innovation Limited Dispositif optoélectronique
EP2850627B1 (fr) 2012-05-18 2016-04-06 Isis Innovation Limited Dispositif optoélectronique comprenant un matériau d'échafaudage poreux et des pérovskites
GB201208793D0 (en) 2012-05-18 2012-07-04 Isis Innovation Optoelectronic device
ES2707296T3 (es) 2012-09-18 2019-04-03 Univ Oxford Innovation Ltd Dispositivo optoelectrónico
CN103000941B (zh) * 2012-11-29 2016-06-01 东莞新能源科技有限公司 凝胶电解液的配方及使用该配方制备凝胶电解液的方法
CN103021667B (zh) * 2012-12-28 2019-02-26 北京石油化工学院 用于染料敏化太阳能电池的原位化学交联凝胶电解质及其制备方法
CN103963212B (zh) * 2013-01-25 2017-05-24 常州亚玛顿股份有限公司 太阳能电池组件的制造方法
JP5972811B2 (ja) 2013-02-22 2016-08-17 富士フイルム株式会社 光電変換素子、光電変換素子の製造方法および色素増感太陽電池
PT3105811T (pt) * 2014-02-12 2018-06-07 Univ Aarhus Célula de escoamento redox recarregável solar
JP2019117889A (ja) * 2017-12-27 2019-07-18 太陽誘電株式会社 色素増感太陽電池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0888030A (ja) * 1994-07-19 1996-04-02 Showa Denko Kk 湿式太陽電池およびその製造方法
JP2000306605A (ja) * 1999-04-22 2000-11-02 Dainippon Ink & Chem Inc 活性エネルギー線硬化性高分子固体電解質およびその製造方法
JP2001110462A (ja) * 1999-10-04 2001-04-20 Hitachi Maxell Ltd 光電変換素子及びその製造方法
JP2001313074A (ja) * 2000-04-27 2001-11-09 Hitachi Chem Co Ltd ゲル状イオン伝導性電解質並びにそれを用いた電池及び電気化学的デバイス
JP2002042879A (ja) * 2000-07-26 2002-02-08 Hitachi Chem Co Ltd 高分子電解質ワニス、これを用いた高分子電解質、複合電極、高分子電解質エレメント又は電気化学的デバイス
WO2002078115A1 (fr) 2001-03-26 2002-10-03 Sharp Corporation Pile solaire sensibilisee par un colorant

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4585581A (en) * 1981-10-19 1986-04-29 The United States Of America As Represented By The United States Department Of Energy Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity
GB2195643B (en) * 1986-07-21 1990-08-15 Yokohama Rubber Co Ltd Uv-curable resin compositions
US5622791A (en) * 1995-08-25 1997-04-22 Valence Technology, Inc. Photoelectrochemical cell
US6291763B1 (en) * 1999-04-06 2001-09-18 Fuji Photo Film Co., Ltd. Photoelectric conversion device and photo cell
JP3946947B2 (ja) 1999-09-24 2007-07-18 株式会社東芝 光増感型太陽電池用電解質組成物、光増感型太陽電池及び光増感型太陽電池の製造方法
JP2001115134A (ja) 1999-10-14 2001-04-24 Nippon Mitsubishi Oil Corp イオン伝導性物質
JP2001273938A (ja) 2000-03-28 2001-10-05 Hitachi Maxell Ltd 光電変換素子
JP2002289271A (ja) 2001-03-26 2002-10-04 Sharp Corp 色素増感型太陽電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0888030A (ja) * 1994-07-19 1996-04-02 Showa Denko Kk 湿式太陽電池およびその製造方法
JP2000306605A (ja) * 1999-04-22 2000-11-02 Dainippon Ink & Chem Inc 活性エネルギー線硬化性高分子固体電解質およびその製造方法
JP2001110462A (ja) * 1999-10-04 2001-04-20 Hitachi Maxell Ltd 光電変換素子及びその製造方法
JP2001313074A (ja) * 2000-04-27 2001-11-09 Hitachi Chem Co Ltd ゲル状イオン伝導性電解質並びにそれを用いた電池及び電気化学的デバイス
JP2002042879A (ja) * 2000-07-26 2002-02-08 Hitachi Chem Co Ltd 高分子電解質ワニス、これを用いた高分子電解質、複合電極、高分子電解質エレメント又は電気化学的デバイス
WO2002078115A1 (fr) 2001-03-26 2002-10-03 Sharp Corporation Pile solaire sensibilisee par un colorant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1494246A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100567330B1 (ko) 2004-08-04 2006-04-04 한국전자통신연구원 이중구조의 염료감응 태양전지
EP1699063A1 (fr) * 2005-03-03 2006-09-06 Fuji Photo Film Co., Ltd. Semiconducteur avec une substance adsorbée
US7446923B2 (en) 2005-03-03 2008-11-04 Fujifilm Corporation Semiconductor, functional device, electrochromic device, optical device, and image-taking unit

Also Published As

Publication number Publication date
KR101005570B1 (ko) 2011-01-05
EP1494246A4 (fr) 2006-11-22
CN1653558A (zh) 2005-08-10
KR20040108722A (ko) 2004-12-24
JP4010170B2 (ja) 2007-11-21
CN100380530C (zh) 2008-04-09
US20050263182A1 (en) 2005-12-01
US7880082B2 (en) 2011-02-01
JP2003303630A (ja) 2003-10-24
EP1494246A1 (fr) 2005-01-05
EP1494246B1 (fr) 2012-04-04
AU2003227481A1 (en) 2003-10-20

Similar Documents

Publication Publication Date Title
WO2003085680A1 (fr) Electrolyte solide, convertisseur photoelectrique et procede pour produire celui-ci
JP4470370B2 (ja) 光電変換素子の製造方法
JP4635474B2 (ja) 光電変換素子、及びこれに用いる透明導電性基板
JP4674435B2 (ja) 光電変換素子
WO2005112183A1 (fr) Élément de conversion photoélectrique et électrode semiconductrice
JP4591131B2 (ja) 色素増感光電変換素子およびその製造方法ならびに電子装置およびその製造方法ならびに電子機器
JP5066792B2 (ja) 色素増感光電変換素子、色素増感光電変換素子の製造方法、光電変換素子モジュール、電子機器、移動体および発電システム
EP2175516A1 (fr) Élément de conversion photoélectrique sensibilisé à une matière colorante, processus de production de l'élément de conversion photoélectrique sensibilisé à une matière colorante, équipement électronique, électrode semi-conductrice, et processus de
JP2007200796A (ja) 光電変換装置及びゲル化剤
WO2004068627A1 (fr) Élément de conversion photoélectrique et son procédé de production, appareil électronique et son procédé de production, et couche semi-conductrice et son procédé de formation
CN103021667B (zh) 用于染料敏化太阳能电池的原位化学交联凝胶电解质及其制备方法
JP4678125B2 (ja) 光電変換素子およびその製造方法ならびに電子装置およびその製造方法
JP2004319130A (ja) 光電変換素子の製造方法、光電変換素子、電子装置の製造方法、電子装置、半導体微粒子層の形成方法および積層構造体
JP2005310445A (ja) ゲル状電解質およびそれを用いた電気化学素子
JP2002184478A (ja) 電解質、光電変換素子、光電気化学電池および電解質の製造方法
JP2008041320A (ja) 色素増感太陽電池のための電解質組成物
JP5439869B2 (ja) 光電変換素子およびその製造方法、光センサならびに太陽電池
JP2015115110A (ja) 色素増感太陽電池の製造方法および色素増感太陽電池
CN110828669A (zh) 一种低温介孔碳基钙钛矿太阳能电池及其制备方法
JP2001338700A (ja) 色素増感型太陽電池
JP2013016390A (ja) 光電変換素子及びその製造方法
JP2011187455A (ja) 色素増感光電変換素子、色素増感光電変換素子の製造方法、光電変換素子モジュール、電子機器、移動体および発電システム
JPWO2004109840A1 (ja) 電極およびその形成方法ならびに光電変換素子およびその製造方法ならびに電子装置およびその製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1020047016187

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2003717557

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 20038109018

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 1020047016187

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2003717557

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 10511012

Country of ref document: US